Allergen Depressant And Depression Method

ABSTRACT

The invention provides a means capable of effectively inactivating and removing allergen or a precursor thereof. The invention relates to an allergen-reducing agent containing water and a water-soluble polymer compound having units having hydroxy or carboxy groups wherein at least a part of hydrogen atoms of the hydroxy or carboxy groups are substituted by specific groups containing a polyether group.

TECHNICAL FIELD

The present invention relates to a method of easily removing allergen orits precursor floating in housing space and an allergen-reducing agentused for the method.

FIELD OF THE INVENTION

Allergic diseases attributable to house dust tend to increase in recentyears and become a social problem. Typical examples of house dustcausing allergy can include pollen, mold spores, and dead bodies andexcrements of mites, but these are very fine substances of several totens μm and can thus be stirred up even by simple activity such as humanwalking to contaminate housing space. The house dust stirred up to floatin the space cannot be removed by general cleaning action, so there isan ardent desire for a method of effectively removing house dustfloating in space.

JP-A 2000-264837 discloses an allergen removing agent as a cationicsurfactant-containing composition to be sprayed into space. JP-A2002-128659 discloses a house dust-treating agent sprayed into space toinactivate and/or remove allergen. JP-A 2002-128680 discloses a housedust-treating agent as a polyvinyl alcohol-containing solution to besprayed into space. JP-A 2000-504621 discloses a method of removing afloating particulate substance in a household environment. WP-A 02/28179discloses a composition for making allergen harmless for the case wherethe amount of dust remaining in fibers is 30% or more in a dust controltest and the MIU value by a method of analyzing frictional coefficientis 3.0 or less, and as a specific compound, a polymer compound isdescribed therein. GB-B 2300122 describes a technique of controllingallergen, which includes using a water-soluble polysaccharide such ashydroxypropyl cellulose to allow small mite allergen to adhere to thesurface thereof so as to stabilize the allergen. JP-A 2002-508438describes a domestic composition containing a vehicle and a householdingredient, said vehicle including a hydrophobic modified water-solublepolysaccharide polymer containing both a water-soluble polysaccharidepolymer main chain and a hydrophobic moiety.

WO-A 00/73351 discloses a novel polysaccharide derivative as a compoundhaving an action of stabilizing a hydrophobic substance, wherein ahydrogen atom of a hydroxy group of the polysaccharide is substituted bya group containing a specific polyoxyalkylene group.

SUMMARY OF THE INVENTION

The present invention relates to an allergen-reducing agent containingwater and a water-soluble polymer compound having units having hydroxyor carboxy groups wherein at least a part of hydrogen atoms of thehydroxy or carboxy groups are substituted by groups represented by thefollowing formula (1):—R^(1a)—(OR^(1b))_(p)-A-R^(1c)  (1)wherein R^(1a) is a C1 to C6 alkylene group which may be substitutedwith a hydroxy or oxo group, R^(1b) is a C1 to C6 alkylene group, R^(1c)is a group selected from a C4 to C30 hydrocarbon group which may besubstituted with a hydroxy group, a C1 to C5 sulfoalkyl group which maybe substituted with a hydroxy group, and a hydrocarbon group which has asteroid skeleton, A is a group selected from —O—, —OCO— and —COO—, p is0 to 50 (average number of moles added), and (OR^(1b)) moles whosenumber is p may be the same or different.

The present invention also relates to an allergen-reducing agentcontained in a spray container, which contains the allergen-reducingagent of the present invention introduced into a container provided witha spray device.

The present invention also relates to an allergen-reducing sheetcontaining a flexible sheet impregnated with the allergen-reducing agentof the present invention.

The present invention also relates to a method of reducing allergen,which includes spraying the allergen-reducing agent of the presentinvention into space.

Further, the present invention relates to a method of reducing allergen,which includes spraying or applying the allergen-reducing agent of thepresent invention onto the surface of an object, and before drying,wiping it away with a water-absorbing article, as well as a cleaningmethod which includes carrying out said method and subsequent cleaningby vacuuming or sweeping cleaning.

Furthermore, the present invention relates to a cleaning method whichincludes wiping the surface of an object with an allergen-reducing sheethaving a flexible sheet impregnated with the allergen-reducing agent ofthe present invention and subsequent cleaning by vacuuming or sweepingcleaning.

DETAILED DESCRIPTION OF THE INVENTION

The inactivation and removal of allergic substances cannot besufficiently effected even by the means described in the aboveliteratures.

The object of the present invention is to provide an agent and methodcapable of effectively inactivating and removing allergen or a precursorthereof.

The allergen-reducing agent according to the present invention containsa water-soluble polymer compound (hereinafter, referred to as component(a)) having units having hydroxy or carboxy groups, which is composed inparticular of such units as a main chain wherein a part or the whole ofhydrogen atoms of the hydroxy or carboxy groups are substituted bygroups represented by the formula (1) below. In the present invention,the water solubility of the water-soluble polymer compound in thepresent invention refers to a solubility of 1 wt % or more in water at20° C.—R^(1a)—(OR^(1b))_(p)-A-R^(1c)  (1)wherein R^(1a) is a C1 to C6 alkylene group which may be substitutedwith a hydroxy or oxo group, R^(1b) is a C1 to C6 alkylene group, R^(1c)is a group selected from a C4 to C30 hydrocarbon group which may besubstituted with a hydroxy group, a C1 to C5 sulfoalkyl group which maybe substituted with a hydroxy group, and a hydrocarbon group which has asteroid skeleton, A is a group selected from —O—, —OCO— and —COO—, p is0 to 50 (average number of moles added), and (OR^(1b)) moles whosenumber is p may be the same or different.

R^(1a) is preferably an ethylene group, propylene group, trimethylenegroup, 2-hydroxytrimethylene group, 1-hydroxytrimethylene group,1-oxoethylene group, 1-oxotrimethylene group or 1-methyl-2-oxoethylenegroup, particularly preferably a 2-hydroxytrimethylene group or1-hydroxytrimethylene group. R^(1b) is preferably an ethylene group orpropylene group, R^(1c) is a linear or branched alkyl or alkenyl groupor a C4 to C30 hydrocarbon group such as a hydrocarbon group (preferablya cholesteryl group) having a steroid skeleton, preferably a C5 to C25,more preferably C6 to C20, alkyl group which may be substituted with ahydroxy group, or a 2-sulfoethyl group, 3-sulfopropyl group,3-sulfo-2-hydroxypropyl group or 2-sulfo-1-(hydroxymethyl)ethyl group. Ais preferably —O—, p is preferably a number of 0 to 40, more preferably0 to 30, even more preferably 0 to 20, even more preferably 10 to 20(average number of moles added).

The water-soluble polymer serving as the component (a) includespolysaccharides such as cellulose, starch, guar gum, xanthane gum,pullulan, dextran, cluster dextrin, fructan, mannan, agar, carrageenan,chitin, chitosan, pectin, alginic acid, hyaluronic acid, inulin etc.;and derivatives thereof substituted with a methyl group, ethyl group,hydroxyethyl group, hydroxypropyl group etc. Its constituentmonosaccharide residue may be substituted with one or more of thesesubstituent groups. Examples of the polysaccharide derivatives includehydroxyethyl cellulose, hydroxyethylethyl cellulose, hydroxyethyl guargum, hydroxyethyl starch, methyl cellulose, methyl guar gum, methylstarch, ethyl cellulose, ethyl guar gum, ethyl starch, hydroxypropylcellulose, hydroxypropyl guar gum, hydroxypropyl starch,hydroxyethylmethyl cellulose, hydroxyethylmethyl guar gum,hydroxyethylmethyl starch, hydroxypropylmethyl cellulose,hydroxypropylmethyl guar gum, hydroxypropylmethyl starch etc. Thesepolysaccharides or derivatives thereof are preferably cellulose, starch,hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, hydroxypropylcellulose, inulin, chitosan, cluster dextrin and guar gum, particularlypreferably hydroxyethyl cellulose, inulin, chitosan, cluster dextrin andguar gum. The substituent group of the polysaccharide derivative canfurther be substituted with a hydroxy group such as a hydroxyethyl groupor hydroxypropyl group to form, for example, a polyoxyethylene chain orthe like thereby attaining a substitution degree of 3.0 or more perconstituent monosaccharide residue, and the substitution degree perconstituent monosaccharide residue is preferably 0.1 to 10.0, morepreferably 0.5 to 5.0.

In the present invention, the component (a) is a polymer compoundwherein a part or the whole of hydrogen atoms of hydroxy groups orcarboxy groups in the water-soluble polymer described above aresubstituted by the substituent groups of the formula (1), and the degreeof substitution with the substituent group (1) is preferably in therange of 0.0001 to 1, more preferably 0.0005 to 0.5, even morepreferably 0.001 to 0.1, even more preferably 0.001 to 0.05, per monomerunit residue containing a hydroxy or carboxy group (for example, perconstituent monosaccharide residue). When R^(1c) in the formula (1) is asulfoalkyl group, the degree of substitution on the sulfoalkyl group ispreferably in the range of 0 to 1, more preferably 0 to 0.8, even morepreferably 0 to 0.5, per monomer unit residue containing a hydroxy orcarboxy group (for example, per constituent monosaccharide residue).

The number-average molecular weight of the component (a) is preferably10,000 to 2,000,000, more preferably 50,000 to 1,500,000, even morepreferably 100,000 to 600,000. The weight-average molecular weight canbe determined by gel permeation chromatography (GPC) with polyethyleneglycol as standard.

The weight-average molecular weight of the component (a) can bedetermined by high performance anion exchange chromatography (HPAEC)with a pulse amperometric detector, or by capillary electrophoresis.

Some components (a) in the present invention can be obtained accordingto a method described in WO00/73351 by reacting a cellulose derivativeor a starch derivative with a compound represented byR^(1d)—(OR^(1b))_(p)-A-R^(1c) wherein R^(1d) represents a C3 to C6epoxylated alkyl group, a C1 to C6 halogenated alkyl group which may besubstituted with a hydroxy group, a carboxy group or a C2 to C6carboxyalkyl group, or a derivative thereof, and R^(1b), p, A and R^(1c)each have the same meaning as defined above, if desired, followed bysulfonation with a usual sulfonating agent.

Another water-soluble polymer compound serving as the component (a)includes a polymer compound obtained from a monomer capable of forming aunit having a hydroxy or carboxy group, such as acrylic acid, vinylacetate (production of polyvinyl alcohol) and glycidol, wherein thehydroxy or carboxy group of the polymer compound is substituted with thegroup of the formula (1) above.

In the present invention, the component (a) is preferably the followingpolymer compound (A) or (B):(A): a water-soluble polymer compound containing a monomer unit (a1) ofthe following formula (2) and a monomer unit (a2) of the followingformula (3) wherein the molar ratio of (a1)/(a2) is 1/1500 to 30/100,and the proportion of (a1) and (a2) in total in the molecule is 50 to100 mol % (hereinafter, referred to as polymer compound (A)).

wherein R^(2a) is a hydrogen atom or a C1 to C3 alkyl group, R^(2b) is agroup selected from a hydrogen atom and —COOM (whereupon M is a hydrogenatom, an alkali metal atom or an alkaline earth metal atom), R^(2c) is agroup selected from a hydrogen atom, a C1 to C3 alkyl group and ahydroxy group, R^(2d) is a C1 to C6 alkylene group which may besubstituted with a hydroxy group, R^(2e) is a C1 to C6 alkylene group,R^(2f) is a C4 to C30 hydrocarbon group which may be substituted with ahydroxy group, B is a group selected from —O—, —COO—, —OCO— and—CONR^(2g)— (whereupon R^(2g) is a hydrogen atom, a C1 to C3 alkyl groupor a C1 to C3 hydroxyalkyl group), and E is a group selected from —O—,—OCO— and —COO—, and q is 0 to 50 (average number of moles added), and(OR^(2c)) moles whose number is q may be the same or different; and

wherein R^(3a) is a hydrogen atom or a C1 to C3 alkyl group, R^(3b) is agroup selected from a hydrogen atom and —COOM (whereupon M is a hydrogenatom, an alkali metal atom or an alkaline earth metal atom), R^(3c) is agroup selected from a hydrogen atom, a C1 to C3 alkyl group and ahydroxy group, G is —COOM, —OH, -T-(R^(3d)O)_(c)—H,—CON(R^(3e))(R^(3f)), —COO—R^(3g)—N⁺(R^(3h)) (R^(3i))(R^(3j)).X⁻,—COO—R^(3g)—N(R^(3h))(R^(3i)), —CON(R^(3e))—R^(3g)—N⁺(R^(3h))(R^(3i))(R^(3j)).X⁻, —CON(R^(3e))—R^(3g)—N(R^(3h))(R^(3j)), or a 5- or6-memberred heterocyclic group having at least one amino or amide groupin the ring, wherein M is a hydrogen atom, an alkaline metal atom or analkaline earth metal atom, and T is a group selected from —O— and —COO—,R^(3d) is a C1 to C6 alkylene group, R^(3e), R^(3f), R^(3h), R^(3i) andR^(3j) each represent a hydrogen atom, a C1 to C3 alkyl group or a C1 toC3 hydroxyalkyl group, R^(3g) is a C1 to C5 alkylene group, X⁻represents an organic or inorganic anion group, and c is 1 to 50(average number of moles added), and (R^(3d)O) moles whose number is cmay be the same or different.(B): a polymer compound containing a monomer unit (a3) of the followingformula (4) and/or the following formula (5) and a monomer unit (a4) ofthe following formula (6) and/or the following formula (7) wherein themolar ratio of (a4)/(a3) is 30/100 to 1/1500, and the proportion of (a4)and (a3) in total in the molecule is 50 to 100 mol % (hereinafter,referred to as polymer compound (B)).

wherein each of J and M is a group selected from —O—, —OCO— and —COO—,each of R^(6a) and R^(7a) is a C1 to C6 alkylene group, each of R^(6b)and R^(7b) is a C1 to C6 alkylene group, each of R^(6c) and R^(7c) is aC4 to C30 hydrocarbon group which may be substituted with a hydroxygroup, each of L and Q is a group selected from —O—, —OCO— and —COO—,and each of r and s is 0 to 50 (average number of moles added), and(OR^(6b)) moles whose number is r or (OR^(7b)) moles whose number is smay be the same or different.<Polymer Compound (A)>

In the formula (2), each of R^(2a) and R^(2b) is preferably a hydrogenatom, and R^(2c) is preferably a hydrogen atom or a methyl group. R^(2f)is preferably a C10 to C24 alkyl or alkenyl group, more preferably a C10to C18 alkyl group. B is preferably —O—, —COO— or —CONR^(2g)— whereinR^(2g) is preferably a hydrogen atom. R^(2d) is a group selected from anethylene group, a propylene group or —CH₂CH(OH)CH₂—, and R^(2e) is agroup selected from an ethylene group, a propylene group or—CH₂CH(OH)CH₂—, preferably an ethylene group. E is preferably —O—, and qis preferably a number of 0 to 40, more preferably 0 to 30, even morepreferably 0 to 20, even more preferably 10 to 20 (average number ofmoles added).

In the formula (3), each of R^(3a) and R^(3b) is preferably a hydrogenatom, R^(3c) is preferably a hydrogen atom or a methyl group. Each ofR^(3e), R^(3f), R^(3h)R^(3i) and R^(3j) is preferably a hydrogen atom,methyl group, ethyl group or hydroxyethyl group, and particularly eachof R^(3f), R^(3h), R^(3i) and R^(3j) is even more preferably a methylgroup, and R^(3e) is even more preferably a hydrogen atom or a methylgroup. R^(3g) is preferably an ethylene group or a propylene group. Theheterocyclic group can include a pyrrolidone group, pyridine group andimidazole group, among which a pyrrolidone group is preferable. X⁻ is achlorine ion, sulfate ion, C1 to C3 alkyl sulfate ion, C1 to C12 fattyacid ion, benzenesulfonate ion which may be substituted with one tothree C1 to C3 alkyl groups, and is preferably a chlorine ion or ethylsulfate ion.

The polymer compound (A) has monomer units (a1) and (a2) representedrespectively by the formulae (2) and (3) wherein (a1) and (a2) arecontained in a (a1)/(a2) molar ratio of 1/1500 to 30/100, preferably1/1200 to 10/100, more preferably 1/1000 to 5/100.

The polymer compound (A) can be obtained according to a known methodsuch as radical polymerization by copolymerizing monomer (a1′) andmonomer (a2′) from which the vinyl monomer units (a1) and (a2) arederived. The vinyl monomer unit (a1) can also be introduced by reactingZ-(OR^(2c))_(q)-E-R^(2f) with a polymer compound obtained bycopolymerizing a polymerizable monomer (a1″) represented byC(R^(2a))(R^(2b))═C(R^(2c))(Y′) with a monomer from which the monomerunit (a2) is derived. Y′ and Z are a reaction group which reacts to formB—R^(2d)—(OR^(2e))_(q)-E-R^(2f).

Specific examples of the vinyl monomer unit (a1′) from which (a1) isderived can include the following compounds:

CH₂═CH—COO—C₂H₄—(OC₂H₄)_(q)—O—R^(2f)

CH₂═CH—COO—CH₂CH(OH)CH₂—(OC₂H₄)_(q)—O—R^(2f)

CH₂═C(CH₃)—COO—C₂H₄—(OC₂H₄)_(q)—O—R^(2f)

CH₂═C(CH₃)—COO—CH₂CH(OH)CH₂—(OC₂H₄)_(q)—O—R^(2f)

CH₂═C(CH₃)—CONH—C₂H₄—(OC₂H₄)_(q)—O—R^(2f)

Specific examples of the vinyl monomer unit (a2′) from which (a2) isderived can include the following compounds: (meth)acrylic acid, maleicacid, α-hydroxyacrylic acid, polyoxyalkylene wherein the average numberof moles added is 2 to 50, preferably 2 to 40, more preferably 2 to 30,even more preferably 2 to 20, even more preferably 10 to 20 (preferablyethylene)mono(meth)acrylate, dialkyl(meth)acrylate (C1 to C3) amide,(meth)acrylic acid mono(di)alkanol (C2 to C3) amide, vinyl acetate whichcan be converted into a vinyl alcohol structure by saponification afterpolymerization, N-(meth)acryloyloxyalkyl (C1 to C3)-N,N-dialkyl (C1 toC3) amine, N-(meth)acryloyloxyalkyl (C1 to C3)-N,N,N-dialkyl (C1 to C3)ammonium salt, N-(meth)acryloylaminoalkyl (C1 to C3)-N,N-dialkyl (C1 toC3) amine, N-(meth)acryloylaminoalkyl (C1 to C3)-N,N-dialkanol (C1 toC3) amine, N-(meth)acryloylaminoalkyl (C1 to C3)-N,N,N-dialkyl (C1 toC3) ammonium salt, N-vinylpyrrolidone, N-vinylimidazole, andN-vinyl-2-caprolactam.

The monomer unit (a1) can also be obtained by copolymerizing the monomerselected from (a2′) with vinyl acetate, then saponifying the resultingcopolymer, and reacting a glycidyl ether compound represented by:

with OH of a vinyl alcohol unit of the resulting saponified product.Alternatively, the monomer unit (a1) can be obtained by copolymerizingthe monomer selected from (a2′) with a polyoxyethylene vinyl etherwherein the average number of moles added is 1 to 200, preferably 1 to100, more preferably 1 to 50, and then reacting the product with acompound represented by:

Alternatively, the monomer unit (a1) can be obtained by copolymerizingthe monomer selected from (a2′) with vinyl acetate and then saponifyingthe resulting copolymer, followed by esterification reaction (or esterexchange reaction) between OH of a vinyl alcohol unit of the resultingsaponified product and polyoxyethylene alkyl ether carboxylic acidrepresented by R^(2f)—O—(C₂H₄O)_(q)—CH₂COX′ wherein X′ is —OH, —Cl,—OCH₃ or —OC₂H₄. Alternatively, the monomer unit (a1) can be obtained bycopolymerizing the monomer selected from (a2′) with a polyoxyethylenevinyl ether wherein the average number of moles added is 1 to 200,preferably 1 to 100, more preferably 1 to 50 and subsequentesterification reaction (or ester exchange reaction) of the resultingcopolymer with a carboxylic acid represented by R^(2f)—COX.

The polymer compound (A) is a polymer compound having the vinyl monomers(a1) and (a2) in an amount of 50 to 100 mol %, preferably 60 to 100 mol%, more preferably 70 to 100 mol %, in the molecule, and can also becopolymerized with other monomers capable of copolymerizing with thevinyl monomer (a1′) or (a1″) and (a2′). The copolymerizable monomers caninclude compounds such as ethylene, propylene, N-butylene, isobutylene,N-pentene, 2-methyl-1-butene, N-hexene, 2-methyl-1-pentene,2-ethyl-1-butene, styrene and vinyl toluene.

The polymer compound (A) is produced particularly preferably by aradical polymerization method, and the radical polymerization method canbe carried out in a bulk, solution or emulsion system. The radicalpolymerization may be initiated by heating, and the initiator includesazo-type initiators such as 2,2′-azobis(2-amidinopropane)dihydrochloride, 2,2′-azobis(N,N-dimethyleneisobutylamidine)dihydrochloride etc., hydrogen peroxide, organic peroxides such asbenzoyl peroxide, t-butyl hydroperoxide etc., persulfates such as sodiumpersulfate etc. Alternatively, the polymerization can be initiated byradical initiators other than those mentioned above, for example byredox initiators such as hydrogen peroxide-Fe³⁺ or by irradiation withlights or radiations in the presence and/or absence of aphotosensitizer.

The number-average molecular weight of the polymer compound (A) in thepresent invention is preferably 2,000 to 200,000, more preferably 3,000to 150,000, even more preferably 4,000 to 120,000. The weight-averagemolecular weight can be determined by gel permeation chromatography withpolyethylene glycol as standard.

<Polymer Compound (B)>

The polymer compound (B) preferable as the component (a) in the presentinvention is a polyglyceryl ether compound whose OH groups are partiallygroups represented by J-R^(6a)—(OR^(6b))_(r)-L-R^(6c). By additionreaction of glycidyl ether, the polyglyceryl ether can be produced as arandom addition product having a unit represented by the formula (4)having glycidyl ether added to OH at the position 1 or 3 of the glycerolgroup and a unit represented by the formula (5) having glycidyl etheradded to OH at the position 2 of the glycerol group. The proportion ofthe units of the formulae (4) and (5) can be arbitrarily selectedwithout influencing the effect of the present invention.

The polymer compound (B) can be produced by reaction of a part ofhydroxy groups of the polyglyceryl ether compound containing the unitsof the formulae (4) and (5) with W—(OR^(6b))_(r)-L-R^(6c). In thisformula, W is a group reacting with OH of the polyglyceryl ether to form-J-R^(6a)—(OR^(6b))_(r)-L-R^(6c). Specific examples ofW—(OR^(6b))_(r)-L-R^(6c) can include the following compounds:

wherein X is —OH, —Cl, —OCH₃ or —OC₂H₄.

These compounds can be reacted with OH of the polyglyceryl ether byusing a usually known method, and for example, the compound of theformula (6-1) can be easily reacted by using an alkali such as NaOH orKOH as a catalyst. When the compound of the formula (6-2) is used,well-known esterification reaction or ester exchange reaction can beused.

The polymer compound (B) in the present invention can contain unit (a5)other than the units (a3) and (a4), and specific examples of (a5) caninclude:

wherein n is a number of 0 to 50, m is a number of 0 to 20, and n+m is anumber of 1 to 50.

The molar ratio of (a4)/(a3) in the polymer compound (B) is 1/1500 to30/100, preferably 1/1200 to 10/100, more preferably 1/1000 to 5/100,and the proportion of (a3) and (a4) in total in the molecule is 50 to100 mol %, preferably 60 to 100 mol %, more preferably 70 to 100 mol %.The number-average molecular weight of the polymer compound (B) ispreferably 500 to 20,000, more preferably 1,000 to 10,000, even morepreferably 3,000 to 8,000. The weight-average molecular weight can bedetermined by gel permeation chromatography with polyethylene glycol asstandard.

The component (a) in the present invention, though being a water-solublepolymer compound, partially has a hydrophobic group as R^(1c). On onehand, allergen particularly mite allergen is water-soluble. By using thecomponent (a) in the present invention as an aqueous compositiondissolved in water, allergen contacted with, and dissolved in, theaqueous composition is estimated to have a structure wherein theallergen is included in hydrophobic groups of the component (a) insolution. As a result, the allergen comes to be in a state covered withthe polymer compound thus hardly exhibiting its allergic action; thiscan be regarded as reduction in the allergen.

The allergen-reducing agent of the present invention preferably containsthe component (a) in an amount of 0.005 to 10 wt %, more preferably 0.01to 5 wt %, even more preferably 0.05 to 1 wt %.

Unless the effect of the present invention is hindered, theallergen-reducing agent of the present invention can contain a polymercompound other than the component (a) and can particularly use awater-soluble polymer compound having units having hydroxy or carboxygroups wherein at least a part of hydrogen atoms of the hydroxy orcarboxy groups are substituted by groups represented by the formula (1)above.

The allergen-reducing agent of the present invention not only containsarbitrary ingredients described below, but also water [hereinafter,referred to as component (b)] that is the balance. The water ispreferably as pure as possible, but may be in such a grade as to besubstantially free from contaminant compounds which can act asallergens. Specifically, sterilized water sterilized with chlorine etc.,or ion exchange water or the like from which metal components such ascalcium present in a trace amount were removed, can be used.

The component (b) is incorporated as the balance to serve as a solventfor component (a) etc., and for spraying into space, is incorporatedpreferably in an amount of 60 wt % or more (excluding a propellant), orfor direct spraying onto a solid surface, is incorporated preferably inan amount of 80 wt % or more, more preferably 90 wt % or more, and theupper limit is preferably 99.995 wt % or less.

For the purpose of increasing the drying of liquid droplets sprayed intospace, increasing the drying of the composition contacted with thesurface of an object and improving the stability of the component (a) inthe allergen-reducing agent of the present invention, theallergen-reducing agent preferably contain a water-soluble organicsolvent (hereinafter, referred to as component (c)), more preferably awater-soluble organic solvent forming an azeotropic mixture with waterand having an azeotropic point of lower than 100° C. with water at1013.25 hPa (760 mmHg), and among compounds forming azeotropic mixtureswith water described in Table 8-43 on page II-147 in “Kagaku BinranKisohen” (Handbook of Chemistry, Fundamental Version), 4th edition,edited by the Chemical Society of Japan and published by Maruzen Co.,Ltd., compounds having an azeotropic point of lower than 100° C.,preferably 60 to 90° C., are preferably used. Preferable examples of thecomponent (c) include ethanol, cyclohexane, 2-butanol, cyclohexanol,cyclohexanone, cyclohexane, toluene, 1-butanol, 2-butanol, 1-propanol,2-propanol, 1-hexanol, hexane, 1-heptanol, 1-pentanol, 2-pentanol etc.,and C2 to C7 alcohol compounds are preferable. In particular, ethanol,1-propanol and 2-propanol are even more preferable in respect of theeffect of removing allergen.

The content of the component (c) in the allergen-reducing agent of thepresent invention is preferably 0 to 50 wt %, more preferably 0.5 to 20wt %, even more preferably 1 to 18 wt %. When the allergen-reducingagent of the present invention is used in a method of removing allergenwhich includes applying or spraying the allergen-reducing agent onto therigid surface of flooring or the like and then wiping it off with anabsorbent or in a method of using a flexible sheet (e.g. a nonwovenfabric) impregnated with the allergen-reducing agent of the presentinvention, the incorporation of the component (c) in an amount ofpreferably 8 wt % or less, more preferably 5 wt % or less, into theallergen-reducing agent of the present invention is more preferable thanincreasing the drying speed, in order to make allergen sufficientlyharmless by preferentially dissolving the allergen in, and sufficientlyincorporating it into, the aqueous solution. When the allergen-reducingagent is used in spraying for a method of removing allergen in space,the component (c) is incorporated in an amount of preferably 5 wt % ormore, more preferably 8 to 20 wt %, into the allergen-reducing agent ofthe present invention.

In the present invention, a repellent against arthropods (hereinafter,referred to as component (d)) is preferably contained, and theallergen-reducing agent of the present invention containing thecomponent (d) can be continuously used to repel arthropods such asmites, to reduce the absolute amount of allergic substances derived fromarthropods. The arthropod repellent in the present invention is definedas a substance having a repellent effect on Dermatophagoides farinae,and is a substance by which the degree of repellency of Dermatophagoidesfarinae becomes 50% or more in the following entry inhibition method.

Method of Measuring the Degree of Repellency (Entry Inhibition Method)

Test medium: A 9-cm Petri dish is fixed to an adhesive sheet plate, andabout 10,000 mites (Dermatophagoides farinae) together with a medium areplaced in the dish. In the center of the Petri dish, a Petri dish of 4cm in diameter is then placed, and a paper filter cut in the samediameter is placed in the bottom and impregnated with 0.5 ml of 10 wt %test substance in ethanol. 500 mg feed having a mouse powder feed mixedwith dry yeast is placed in the center of the filter paper.

Comparative medium: A comparative medium is prepared in the same manneras above except that another 9-cm Petri dish is fixed to the sameadhesive sheet plate, and in the test medium, ethanol alone is used asthe solution with which the filter paper is impregnated.

These Petri dishes are placed under the condition of 25° C./75% RH, and48 hours later, mites having entered the feed in the center are counted,and from a difference in count between the test medium and comparativemedium, the degree of repellency (%) is calculated according to thefollowing equation. The mites are counted under a stereoscopicmicroscope.Degree of repellency (%)=(1−number of entering mites in the testmedium/number of entering mites in the comparative medium)×100

A compound preferable in respect of safety as the component (d) in thepresent invention is an extract obtained from a natural material, acompound obtained by isolating, from a natural material, a compoundoccurring in an extract of the natural material, or a compound obtainedby synthesizing a compound occurring in an extract of a naturalmaterial, and a mixture thereof, and specifically the followingcompounds are preferable.

(d-1): a single synthetic or isolated perfume, or a mixture of two ormore perfumes, selected from tetrahydrolinalool, bornyl acetate,myrcenyl acetate, cedryl acetate, lavandulyl acetate, citronellylisobutyrate, terpinyl propionate, linalyl formate, citronellyl tigrate,nopyl acetate, vetiveryl acetate, lyral, citronellyloxyacetaldehyde,2,6,10-trimethyl-9-undecanal, α-ionone, β-ionone, irone, α-damascone,β-damascone, nootkatone, cedryl methyl ether, isomenthone, citronellal,linalool, cintronellol, citral, L-menthol, p-menthane, α-pinene,β-pinene, d-limonene, geraniol, α-terpineol, β-terpineol, γ-terpineol,1,8-cineol, p-menthan-8-ene-1,2-diol, eugenol, benzyl formate, benzylacetate, benzyl propionate, benzyl butyrate, benzyl valerate, benzylcaproate, benzyl phenyl ketone, benzophenone, linalool, α-hexyl succinicaldehyde, coniferyl aldehyde, jasmone, dihydrojasmone, methyl jasmonateand methyl dihydrojasmonate;

(d-2): a single vegetable essential oil, or a mixture of two or morevegetable essential oils, selected from lemon grass oil, lavender oil,orange oil, vetiver oil, patchouli oil, cananga oil, clove oil, cajeputoil, citronella oil, natsumegu oil, pepper oil, sandal wood oil, bulkoil, cagin oil, ginger oil, campo oil, cubeba oil, lemon grass oil, conemint oil, anise oil, lang oil, cinnamon oil, mease oil, palomarosa oil,fennel oil, calamus oil, taimes oil, neam oil, cinnamon leaf oil andcedar wood oil;

(d-3): hinokitiol and/or hinokitiol derivatives; and

(d-4): a plant extract extracted with alcohol from persimmon leaves,Japanese fatsia, mugwort, celery and hottuynia cordata.

In the present invention, the compounds (d-1) and (d-2) are particularlypreferable, and the compound (d-1) is particularly preferably jasmone,dihydrojasmone, methyl jasmonate or methyl dihydrojasmonate, and thevegetable essential oil (d-2) is particularly preferably calamus oil,cinnamon leaf oil, clove oil, lemon grass oil or cedar wood oil.

The allergen-reducing agent according to the present invention containsthe component (d) preferably in an amount of 0.001 to 2 wt %, morepreferably 0.005 to 1 wt %, even more preferably 0.01 to 0.5 wt %. Aperfume component when incorporated in addition to the component (d) isincorporated such that the total amount of the perfume component and thecomponent (d) is preferably 2 wt % or less, more preferably 1 wt % orless, even more preferably 0.5 wt % or less.

In the present invention, a sterilizing agent (hereinafter, referred toas component (e)) is preferably contained, and it adheres to mold sporesetc. known as allergic substances floating in air to prevent propagationof molds etc. and reduce the absolute amount of allergenic substancesderived from the molds.

The antibacterial compound as the component (e) in the present inventionis a compound indicating an inhibition band in an antibacterial testcarried out according to a method JIS L 1902 “Antibacterial Test Methodof Fibrous Products” using a cloth having 1 wt % of the compoundadhering uniformly to cotton calico #2003. The compound can be selectedfrom compounds described on pp. 501-564 in “Kosyohin,Iyakuhinbofu•Sakkinzai No Kagaku” (Science of Perfumes, Cosmetics,Pharmaceutical Preservatives and Bactericidal Agents) (authored byKoichi Yoshimura & Hirofumi Takigawa and published on Apr. 10, 1990 byFlagrance Journal Ltd.).

The component (e) in the present invention is particularly preferablyone of the following antibacterial compounds (1) to (IV):

(I) a quaternary ammonium group-free antibacterial compound (excludingan organic peracid or organic peroxide) having a solubility of 1 g/100 gor lower, preferably 0.5 g/100 g or lower, in water at 20° C., amolecular weight of 100 to 420, preferably 150 to 410, and a meltingpoint of 40° C. or more;

(II) a water-soluble quaternary ammonium antibacterial compound having asolubility of 2 g/100 g or higher, preferably 5 g/100 g or higher, inwater at 0° C. and having at least one C8 to C16 alkyl group;

(III) at least one antibacterial compound selected from2-(4-thiocyanomethylthio) benzimidazole, polylysine, polyhexamethylenebiguanide and glucuronic acid chlorohexizine; and

(IV) a salt of a metal selected from silver, copper and zinc, having asolubility of higher than 1 g/100 g in water at 20° C.

The compound satisfying the properties (I) is preferably at least onemember selected from triclosan, bis-(2-pyridiothio-1-oxide) zinc,2,4,5,6-tetrachloroisophthalonitrile, trichlorocarbanilide,8-oxyquinoline, dehydroacetic acid, benzoic esters, chlorocresols,chlorothymol, chlorophene, dichlorophene, bromochlorophene andhexachlorophene. Particularly, triclosan is preferable because it has anexcellent effect for the object of the present invention. Triclosanderivatives described in JP-A 11-189975 are also favorable, andspecifically dichlorohydroxy diphenyl ether or monochlorohydroxydiphenyl ether is preferable.

As the compound (II), it is also preferable to use a quaternary ammoniumcompound represented by the following formula (8) or (9):

wherein R^(8a) and R^(9a) each represent a C5 to C16, preferably C7 toC16, alkyl group or alkenyl group, preferably alkyl group, R^(8d) andR^(8e) each represent a C1 to C3 alkyl group or hydroxyalkyl group, andT is —COO—, —OCO—, —CONH—, —NHCO— or

n1 is 0 or 1. R^(8b) or R^(8c) is a C1 to C6 alkylene group or—(O—R^(8f))_(m1)— wherein R^(8f) is an ethylene group or propylenegroup, preferably an ethylene group, m1 is a number of 1 to 10,preferably 1 to 5, and Y⁻ is an anion group, preferably a halogen ion,or a C1 to C3 alkyl sulfate ion.

An even more preferable quaternary ammonium compound includes thefollowing compounds. Y⁻ in the formula has the same meaning as definedabove.

-   -   wherein R is a C8 to C16 alkyl group.    -   wherein R is an optionally branched C6 to C10 alkyl group, and k        is a number of 1 to 5.    -   wherein R is a C8 to C18 alkyl group.

The compound (III) is particularly preferably polylysine.

As the compound (IV), a compound having a solubility of higher than 1g/100 g in water at 20° C. can be selected from compounds containingsilver, copper and zinc described on pages II-166 to II-177 and in Table8-42 in “Kagaku Binran Kisohen” (Handbook of Chemistry, FundamentalVersion), 3rd edition. Among these compounds, zinc salts are preferablein the present invention, and particularly a compound selected from zincsulfate, zinc chloride and zinc acetate is preferable.

The component (e) in the present invention is even more preferably atleast one member selected from triclosan, the compound of the formula(8), polylysine, zinc sulfate, zinc chloride and zinc acetate, in orderto achieve a preferable effect on reduction of allergen.

The content of the component (e) in the allergen-reducing agent of thepresent invention is preferably 5 wt % or less, more preferably 0.001 to3 wt %, even more preferably 0.005 to 2 wt %.

The allergen-reducing agent of the present invention is in the form ofan aqueous solution (dispersed component may be present) having thecomponent (a) and, if desired, the components (c) to (e) dissolved inwater of the component (b). The pH value of the allergen-reducing agentof the present invention at 20° C. is preferably 5.5 to 8.5, morepreferably 6.5 to 8.0, from the viewpoint of safety and damage to a basematerial. As a pH adjusting agent, acids, for example inorganic acidssuch as hydrochloric acid and sulfuric acid, organic acids such ascitric acid, succinic acid, malic acid, fumaric acid, tartaric acid,malonic acid and maleic acid, and alkalis, for example alkali metalhydroxides such as sodium hydroxide and potassium hydroxide, carbonatessuch as sodium carbonate and potassium carbonate, ammonia andderivatives thereof, and amine compounds such as monoethanol amine,diethanol amine, triethanol amine, aminomethyl propanol and aminomethylethanol are preferably used alone or as a mixture thereof. In thepresent invention, a substance other than the component (a), whichsolidifies upon drying, is in a solid state at 30° C. or less and doesnot exhibit adhesiveness or film-forming properties, exhibitssolidifying properties with allergens aggregated at the time of drying,and is thus preferably used, for the purpose of improving physicalallergen removability. From the viewpoint of making allergen harmless,the allergen reducing effect can be achieved even if the amount of suchsolidifying substance is less than 0.01 wt %. For allergen on a rigidsurface or in space, the amount of the solidifying substance ispreferably smaller, and the amount of the solidifying substance in theallergen-reducing agent is designed to be incorporated preferably in anamount of 1 wt % or less, more preferably 0.1 wt % or less, even morepreferably 0.05 wt % or less, and accordingly the concentration of thepH adjusting agent is also regulated in consideration of this aspect.The loss by drying (described in JIS K0067, a method of drying underheating at atmospheric pressure, 105° C./2 hours) in theallergen-reducing agent of the present invention is preferably 95% ormore, more preferably 98% or more, even more preferably 99% or more,even more preferably 99.5% or more.

The allergen-reducing agent of the present invention can be blended notonly with the components (a) to (e) but also with a surfactant such asalkyl glucoside other than the component (e), a chelating agent such ascitric acid, a water-soluble solvent for example glycol such asdiethylene glycol monobutyl ether etc., a thickener such as xanthane gumetc., an anti-fungus agent/antiseptic, and a perfume other than thecomponent (c), and in use of these components, there is need forconsideration of the safety and physical properties of theallergen-reducing agent as well as for sufficient consideration ofallergy. The total amount of the components other than the components(a) to (e) is preferably 2 wt % or less, more preferably 1.5 wt % orless, even more preferably 1 wt % or less.

One application form of the allergen-reducing agent of the presentinvention includes the allergen-reducing agent contained in a spraycontainer, which contains the allergen-reducing agent with which acontainer equipped with a spray device is charged. Another applicationform includes an allergen-reducing sheet containing a flexible sheetimpregnated with the allergen-reducing agent of the present invention.This allergen-reducing sheet can be used in a cleaning method whichincludes wiping the surface of an object with the sheet and subsequentcleaning by vacuuming or sweeping cleaning. In connection with this,there is provided the allergen-reducing agent of the present inventionprovided with an indication to the effect that it is used in suchspecific cleaning method, as well as the allergen-reducing sheet of thepresent invention provided with the same indication.

The allergen-reducing agent contained in a spray container is used in amethod of making allergen harmless by spraying it into allergen-floatingspace and in a method of making allergen harmless on the surface of atreatment object by directly spraying it onto the object.

By spraying the allergen-reducing agent from the spray container, it iscontacted with floating allergen or an allergen precursor. A majority ofallergen substances are water-soluble compounds, and these compounds aredissolved in liquid droplets of the allergen-reducing agent andcontacted with the component (a). In the present invention, thecomponent (a) has an effect of inactivating allergen itself in additionto the effect of aggregation/sedimentation described above, and evenafter sedimentation, the contact of allergen with the human body can beprevented to remove allergen and its precursor effectively. Inconnection with this method, the allergen-reducing agent of the presentinvention provided with an indication to the effect that it is used inthe allergen reducing method of spraying into space can be providedaccording to the present invention.

The method of directly spraying the allergen-reducing agent of thepresent invention onto a treatment object is effective particularly forthe rigid surface of a floor or the like, and In this case, theallergen-reducing agent after spraying is wiped off with awater-absorbing article, for example an absorbent such as aliquid-absorbing cloth, before the allergen-reducing agent is not dried,whereby allergen can be removed by absorption into the absorbent.Generally, when one absorbent is repeatedly used in wiping treatment,there is the case where allergen removed once by absorption into theabsorbent adheres again to a rigid surface, so a sufficient allergenreducing effect may not be obtained. In the present invention, however,there is no such problem. This is because even if allergen adheres againto a treatment surface, the allergen dissolved once in theallergen-reducing agent of the present invention has been made harmlessby the component (a). Accordingly, the method described above may use anabsorbent impregnated with the allergen-reducing agent. Theallergen-reducing agent of the present invention is sprayed directlyonto the surface of an object and then dried, which may be followed bycleaning with a cleaner. In this case, the allergen made harmless by thecomponent (a) in the present invention is hardly stirred up and can thusbe easily removed by a cleaner. Generally, allergen is a very lightsubstance and easily scatters even by movement of human, but when theallergen-reducing agent of the present invention is used, there can beobtained an excellent effect of making allergen harmless andsimultaneously preventing scattering.

A spraying method using a propellant such as aerosol as a spray deviceis also feasible, but in the present invention, a trigger sprayer ispreferably used. The trigger sprayer is preferably the one jetting theagent in an amount of 0.1 to 2.0 g, preferably 0.2 to 1.5 g, morepreferably 0.3 to 1.0 g, by one stroke. As the container in the triggersprayer used in the present invention, a pressure-accumulating triggerdisclosed in Japanese Utility Model Application Laid-Open (JP-U) No.4-37554 is particularly excellent in respect of spraying uniformity.

With respect to jetting properties, the trigger sprayer is preferably apressure-accumulating trigger sprayer which sprays a liquid on an areaof 100 to 800 cm², preferably 150 to 600 cm², when an object placedvertically on the ground is sprayed with the liquid from a place apartby 15 cm. In the present invention, the component (a) is sprayedpreferably in an amount of 10 to 4000 mg, more preferably 50 to 4000 mg,per m³ of space, in order to bring about a higher effect of removingallergen.

The sprayer used for spraying into space is a sprayer not foaming theliquid upon spraying, in order to make liquid droplets smaller. Itfollows that preferably the incorporation of a surfactant exhibitingfoaming properties is substantially avoided.

On the other hand, a flexible sheet for impregnation, used in anallergen-reducing sheet impregnated with the allergen-reducing agent, ispreferably a cellulose fiber-containing fiber structure or a laminate offiber structures. The fiber structure includes a nonwoven fabric, awoven fabric and a knit cloth, and in the present invention, a nonwovenfabric is particularly preferably used in respect of cleaningproperties. The cellulose fiber includes naturally occurring fibers suchas cotton and hemp, cellulose-based chemical fibers such as viscousrayon, TENCEL and acetate, and in the present invention, rayon is usedeven more preferably because of an excellent effect of removing allergenetc. Usable fibers other than cellulose fibers include polyolefin fiberssuch as polyethylene (PE) and polypropylene (PP), polyester fibers suchas polyethylene terephthalate, polyamide fibers such as nylon,polyacrylonitrile fibers and polyvinyl alcohol fibers. The thickness ofthe flexible sheet in a dry state is preferably 0.2 to 10 mm, morepreferably 0.4 to 5 mm, under a load of 3 g/m². The flexible sheetpreferably has water retention properties by which water that is 1 to 4times as high as the weight of the sheet can be retained. With respectto the degree of impregnation, the flexible sheet is impregnated withthe allergen-reducing agent in a weight ratio of preferably 1.5 to 5,more preferably 2.2 to 3.5, particularly to the fiber structure. Theamount of the allergen-reducing agent contained in the sheet variesdepending on the fiber diameter and basis weight of the fiber structure.

In the present invention, the fiber structure serving as the flexiblesheet contains cellulose fibers in an amount of preferably 40 to 100 wt%, more preferably 50 to 90 wt %, in the fiber structure.

The density (bulk density) of the fiber structure serving as theflexible sheet is preferably 0.01 to 1.0 g/cm³, more preferably 0.05 to0.5 g/cm³, even more preferably 0.1 to 0.3 g/cm³, under a load of 3.0gf/cm². The basis weight is preferably 5 to 150 g/m², more preferably 10to 100 g/m², even more preferably 20 to 70 g/m².

When a nonwoven fabric is used in the flexible sheet in the presentinvention, mention is made of spun lace, spun bond, melt blown, needlepunch and/or stitch bond in addition to wet nonwoven fabrics and drynonwoven fabrics such as chemical bond, thermal bond (air-through) andair-laid, and particularly one or more members selected from wetnonwoven fabrics, chemical bond, thermal bond (air-through), melt blownand spun lace are effective in respect of the effect of the invention.Low-interweaved nonwoven fabrics composed of fibers having a fiberlength of 20 mm or more, particularly 30 to 100 mm, especially 35 to 65mm, are preferably used.

Such low-interweaved nonwoven fabrics include spun lace nonwovenfabrics, thermal bond nonwoven fabrics such as air-through, spun bondnonwoven fabrics, and three-dimensionally raised nonwoven fabrics. Inthis case, a low-interweaved nonwoven fabric composed of fibers having afiber length of 20 mm or more does not require the fiber lengths of allconstituent fibers to be 20 mm or more, and incorporation of fibers witha fiber length of less than 20 mm inevitably mixed and/or generated in astarting material of the nonwoven fabric and/or in the productionprocess is allowed. Formation of a large number of embossed portions onthe surface of the wiping material of the present invention by thermalembossing is preferable in respect of improvement in operativeness atthe time of cleaning (reduction in frictional resistance).

The present invention also provides the following cleaning method forreducing allergen. That is, the cleaning method includes spraying orapplying the allergen-reducing agent of the present invention onto thesurface of an object before cleaning by vacuuming or sweeping cleaningand then wiping it off with a water-absorbing article before theallergen-reducing agent is dried. Cleaning by vacuuming or sweepingcleaning causes allergen to be scattered, and thus a more sufficienteffect can be obtained by previous allergen reducing treatment than byallergen reducing treatment after cleaning. The cleaning method of thepresent invention unlike conventional wiping cleaning involves treatinga rigid surface with the allergen-reducing agent of the presentinvention prior to the cleaning, whereby excellent removability ofallergen can be achieved. For the water-absorbing article used inwiping, the description of the flexible sheet can be referred to. Themethod of the present invention also involves wiping a water-absorbingarticle impregnated with the allergen-reducing agent of the presentinvention. In connection with this, the present invention provides theallergen-reducing agent of the present invention provided with anindication to the effect that it is used in such specific cleaningmethod.

The allergen-reducing agent contained in a spray container is used in amethod of directly spraying it onto a treatment object to make allergenharmless on the surface of the object. As used herein, the surface ofthe object refers to any surface to which allergen can adhere, andincludes the floor surface of flooring, a cushion floor, a tatami matetc. and the surface of furniture made of wood, leather, glass, metaland plastics and the surface of electrical appliances and coatedsurfaces thereof.

As the water-absorbing article, it is possible to use a liquid-absorbingarticle, for example a cloth such as a dustcloth etc., a nonwovenfabric, and a porous article such as sponge and paper. Particularly, anonwoven fabric and sponge are preferable in respect of operativenessand the amount of retainable liquid, and the form is preferably a sheetshape or roller shape. Generally, when one absorbent is used repeatedlyin wiping treatment, there is the case where allergen removed once byabsorption into the absorbent adheres again to a rigid surface, and thusa sufficient allergen reducing effect may not be obtained. In thepresent invention, however, there is no such problem. This is becauseeven if allergen adheres again to a treatment surface, the allergendissolved once in the allergen-reducing agent of the present inventionhas been made harmless by the component (a). Accordingly, the methoddescribed above may use an absorbent impregnated with theallergen-reducing agent. As a matter of course, a means for preventingre-adhesion is preferably taken, and in this case, an absorbentcontaining cellulose fibers is preferably used, and specifically a fiberstructure containing cellulose fibers described later can be used.

As described above, the allergen-reducing agent of the present inventionis used in the allergen reducing method which includes spraying orapplying it onto the surface of an object and then wiping it off with awater-absorbing article before the allergen-reducing agent is dried, andthus the present invention also provides the allergen-reducing agent ofthe present invention provided with an indication to the effect that itis used in the specific allergen reducing method.

The present invention provides a cleaning method wherein before cleaningby vacuuming or sweeping cleaning, the allergen-reducing agent of thepresent invention is sprayed or applied onto the surface of an objectand wiped off with a water-absorbing article before drying (hereinafter,referred to as cleaning method 1). The present invention also provides acleaning method wherein the surface of an object is wiped with theabove-described allergen-reducing sheet having a flexible sheetimpregnated with the allergen-reducing agent of the present inventionand then cleaned by vacuuming or by sweeping (hereinafter, referred toas cleaning method 2). Cleaning by vacuuming or sweeping cleaning causesallergen to be scattered, so a more sufficient effect can be obtained byprevious allergen reducing treatment than by allergen reducing treatmentafter cleaning. Particularly, the cleaning method 1 of the presentinvention unlike conventional wiping cleaning involves treating a rigidsurface with the allergen-reducing agent of the present invention priorto the cleaning, whereby excellent removability of allergen can beachieved. For the water-absorbing article used in wiping, thedescription of the flexible sheet can be referred to. The presentinvention also includes a method of wiping with a water-absorbingarticle impregnated with the allergen-reducing agent of the presentinvention. In connection with this, the present invention provides theallergen-reducing agent of the present invention provided with anindication to the effect that it is used in the specific cleaning method1 or 2.

When the allergen-reducing agent of the present invention is appliedonto the surface of an object, a cloth such as a dustcloth, a nonwovenfabric, a porous article such as sponge or paper, or an article such asa brush capable of retaining liquid can be used, or theallergen-reducing agent can be applied by hand or with a device such asa spatula, scraper or roller. Particularly, a nonwoven fabric and spongeare preferable in respect of operativeness and the amount of retainableliquid, and the form is preferably a sheet shape or roller shape.

When R^(1c) is a hydrocarbon group having a steroid skeleton, thefollowing compounds can also be used in the allergen-reducing agent andmethod of the present invention.

That is, the present invention provides a cholesteryl polysaccharidederivative wherein a part or all of hydrogen atoms of hydroxy groups ina polysaccharide or its derivative are substituted by the followinggroup (A):

(A) Group represented by the following formula (1p) [hydrogen atom of ahydroxy group of the substituent group (A) may be further substituted bythe substituent group (A)]-E¹-(OA)n-E²-R  (1p)wherein E¹ represents a C1 to C6 linear or branched divalent saturatedhydrocarbon group whose hydroxy group or oxo group may be substituted, nis a number of 5 to 30, A's whose number is n are the same or differentand each represent a C1 to C6 linear or branched divalent saturatedhydrocarbon group, E² represents an ether linkage or an oxycarbonylgroup (—OCO— or —COO—) and R represents a hydrocarbon group having asteroid skeleton, as well as a process for producing the same.

Further, the present invention provides a process for producing thepolysaccharide derivative of the present invention, which includesreacting a polysaccharide or its derivative with a polyoxyalkylenatingagent represented by (a) the following formula (3p):E³-(OA)_(n)-E²-R  (3p)wherein E³ is a C3 to C6 epoxylated alkyl group, a C1 to C6 linear orbranched halogenated alkyl group whose hydroxy group may be substituted,a carboxy group, or a C2 to C6 carboxyalkyl group or a derivativethereof, n is a number of 5 or 30, A's whose number is n are the same ordifferent and each represent a C1 to C6 linear or branched divalentsaturated hydrocarbon group, E² represents an ether linkage oroxycarbonyl group (—OCO— or —COO—) and R represents a hydrocarbon grouphaving a steroid skeleton.

When cellulose is used as the polysaccharide or its derivative, therepeating unit of the polysaccharide derivative of the present inventionis represented by the following formula:

wherein R's are the same or different and each represent a groupselected from (1) a hydrogen atom, methyl group, ethyl group,hydroxyethyl group and hydroxypropyl group, (2) a substituent group (A)containing a polyoxyalkylene group, (3) a sulfoalkyl group (B), (4) acarboxyalkyl group (C), and (5) a cationic substituent group (D), Q'sare the same or different and each represent a C2 to C4 alkylene group,and a, b and c are the same or different and each represent a number of0 to 10. The QO group, R group, a, b and c in the repeating unit oramong the repeating units may be the same or different, and hydroxygroups of the substituent groups (A) to (D) may be further substitutedwith other substituent groups (A) to (D), provided that the repeatingunit has at least the substituent group (A) as R.

E¹ in the formula (1p) for the substituent group (A) containing apolyoxyalkylene group is preferably a C2 or C3 group, and preferableexamples include ethylene, propylene, trimethylene,2-hydroxytrimethylene, 1-hydroxymethylethylene, 1-oxoethylene,1-oxotrimethylene, 1-methyl-2-oxoethylene etc.

A in the formula (1p) is preferably a C2 or C3 group, and preferableexamples include ethylene, propylene and trimethylene. Thepolymerization degree of (—OA-), represented by n, is preferably 5 to30, more preferably 5 to 25, in respect of the thickening effect andemulsion stability, and A's whose number is n may be the same ordifferent. n is meant to be the average number of moles added. E² is anether linkage or an oxycarbonyl group, preferably an ether linkage.

R in the formula (1p) is a hydrocarbon group having a steroid skeleton,particularly preferably a cholesteryl group.

The degree of substitution with the substituent group (A) in thepolysaccharide derivative of the present invention is preferably in therange of 0.0001 to 1.0, more preferably 0.0005 to 0.5, even morepreferably 0.001 to 0.1.

The polysaccharide derivative of the present invention may besubstituted with one or more groups selected from the followingsubstituent group (B), (C) and (D), in addition to the substituent group(A). Hydrogen atoms of hydroxy groups of the substituent groups (A) to(D) may further be substituted with one or more groups selected from thesubstituent groups (A) to (D).

(B) C1 to C5 sulfoalkyl group whose hydroxy group may be substituted, ora salt thereof.

The substituent group (B) includes a 2-sulfoethyl group, 3-sulfopropylgroup, 3-sulfo-2-hydroxypropyl group, 2-sulfo-1-(hydroxymethyl)ethylgroup etc., among which a 3-sulfo-2-hydroxypropyl group is preferablefrom the viewpoint of stability and producibility. All or a part ofthese substituent groups (B) may be salts with the group 1 or 2 elementssuch as Na, K, Ca and Mg or organic cations such as amines, ammoniumetc. The degree of substitution with these substituent groups (B) ispreferably in the range of 0 to 1.0, more preferably 0 to 0.8, even morepreferably 0 to 0.5, per constituent monosaccharide residue.

(C)C2 to C6 carboxyalkyl group whose hydroxy group may be substituted,or a salt thereof.

The substituent group (C) includes a carboxymethyl group, carboxyethylgroup, carboxypropyl group, carboxybutyl group and carboxypentyl group,among which a carboxymethyl group is preferable from the viewpoint ofstability and productivity. All or a part of these substituent groups(C) may be salts with the group 1 or 2 elements such as Na, K, Ca and Mgor organic cations such as amine, ammonium etc. The degree ofsubstitution with these substituent groups (C) is preferably in therange of 0 to 1.0, more preferably 0 to 0.8, even more preferably 0 to0.5, per constituent monosaccharide residue. (D) Group represented bythe following formula (2p):

wherein D¹ represents a C1 to C6 linear or branched divalent saturatedhydrocarbon group whose hydroxy group may be substituted, R¹, R² and R³are the same or different and each represent a C1 to C3 linear orbranched alkyl group whose hydroxy group may be substituted, and X⁻represents a hydroxy ion, halogen ion or organic acid ion.

D1 in the cationic substituent group (D) is preferably a C2 or C3 group,and preferable examples include ethylene, propylene, trimethylene,2-hydroxytrimethylene, 1-hydroxymethylethylene etc.

R¹, R² and R³ in the cationic substituent group (D) include a methylgroup, ethyl group, propyl group, 2-hydroxyethyl group etc., among whicha methyl group and ethyl group are preferable.

The halogen ion represented by X⁻ in the cationic substituent group (D)includes a chlorine ion, bromine ion, iodine ion etc., and the organicacid ion represented by X⁻ includes CH₃COO⁻, CH₃CH₂COO⁻, CH₃(CH₂)₂COO⁻,etc. X⁻ is preferably a hydroxy ion, chlorine ion or bromine ion.

The degree of substitution with these cationic substituent groups (D) ispreferably in the range of 0 to 0.5, more preferably 0 to 0.3, perconstituent monosaccharide residue.

The polysaccharide derivative of the present invention can be producedfor example by reacting a polysaccharide or a derivative thereof with:

(a) a polyoxyalkylenating agent represented by the following formula(3p):E³-(OA)n-E²-R  (3p)wherein E³ represents a C3 to C6 epoxylated alkyl group, a C1 to C6linear or branched halogenated alkyl group whose hydroxy group may besubstituted, a carboxy group or a C2 to C6 carboxyalkyl group, or aderivative thereof, and n, A, E² and R each have the same meaning asdefined above, or further reacting it with one or more compoundsselected from the following (b), (c) and (d):(b) a sulfonating agent selected from vinylsulfonic acid, a C1 to C5haloalkanesulfonic acid whose hydroxy group may be substituted, C2 to C6sulfonic acid having an epoxy group, and a salt thereof,(c) a carboxylating agent selected from C2 to C6 halogenated carboxylicacid whose hydroxy group may be substituted and a salt thereof, and(d) a cationizing agent represented by the following formula (4p):

wherein D² is a C3 to 6 epoxylated alkyl group or a C1 to C6 linear orbranched halogenated alkyl group which may have a hydroxy group and R¹,R², R³ and X⁻ each have the same meaning as defined above.

That is, the polysaccharide derivative of the present invention isobtained by polyoxyalkylenating all hydrogen atoms of hydroxy groups ina polysaccharide or a derivative thereof (introduction of substituentgroup (A)) or by polyoxyalkylenating a part of the hydrogen atoms(introduction of substituent group (A)), if necessary followed bysulfonation (introduction of sulfoalkyl group (B)), carboxylation(introduction of carboxyalkyl group (C)) and cationization (introductionof cationic substituent group (D)). The polyoxyalkylenating reaction,sulfonating reaction, carboxylating reaction and cationizing reactionmay be carried out in any order, or 2 to 4 reactions can be carried outsimultaneously, but the reactions are carried out preferably in theorder of the polyoxyalkylenating reaction, cationizing reaction,carboxylating reaction and sulfonating reaction.

The polysaccharide used in the present invention or a derivative thereofincludes polysaccharides such as cellulose, guar gum, starch, pullulan,dextran, fructan, mannan, agar, carrageenan, chitin, chitosan, pectin,alginic acid, hyaluronic acid and inulin, as well as derivatives thereofsubstituted with a methyl group, ethyl group, hydroxyethyl group,hydroxypropyl group etc. The constituent monosaccharide residue may besubstituted with one or more of these substituent groups, and examplesof the polysaccharide derivatives include hydroxyethyl cellulose,hydroxyethylethyl cellulose, hydroxyethyl guar gum, hydroxyethyl starch,methyl cellulose, methyl guar gum, methyl starch, ethyl cellulose, ethylguar gum, ethyl starch, hydroxypropyl cellulose, hydroxypropyl guar gum,hydroxypropyl starch, hydroxyethylmethyl cellulose, hydroxyethylmethylguar gum, hydroxyethylmethyl starch, hydroxypropylmethyl cellulose,hydroxypropylmethyl guar gum, hydroxypropylmethyl starch etc. Thesepolysaccharides or derivatives thereof are preferably cellulose, starch,hydroxyethyl cellulose, methyl cellulose, ethyl cellulose andhydroxypropyl cellulose, and particularly hydroxyethyl cellulose ispreferable. The substituent group on the polysaccharide derivative canfurther be substituted with a hydroxy group such as a hydroxyethyl groupor hydroxypropyl group to form, for example, a polyoxyethylene chain orthe like thereby attaining a substitution degree of higher than 3.0 persubstituent monosaccharide residue, and the substitution degree perconstituent monosaccharide residue is preferably 0.1 to 10.0, morepreferably 0.5 to 5.0. The weight-average molecular weight of thepolysaccharide or a derivative thereof is preferably in the range of1000 to 10000000, more preferably 10000 to 5000000, even more preferably10000 to 2000000.

Hereinafter, the polyoxyalkylenating reaction, sulfonating reaction,carboxylating reaction and cationizing reaction are describedrespectively in more detail.

(Polyoxyalkylenating Reaction)

The polyoxyalkylenating reaction of the polysaccharide or a derivativethereof is carried out by dissolving or dispersing the polysaccharide ora derivative thereof in a suitable solvent and reacting it with thepolyoxyalkylenating agent (a) represented by the formula (3p) above.

Among the groups represented by E³ in the formula (3p), the C3 to C6epoxylated alkyl group includes a 2,3-epoxypropyl group, 3,4-epoxybutylgroup, 4,5-epoxypentyl group, 5,6-epoxyhexyl group etc. The C1 to C6linear or branched halogenated alkyl group whose hydroxy group may besubstituted includes a 2-chloroethyl group, 3-chloropropyl group,4-chlorobutyl group, 6-chlorohexyl group, 2-bromoethyl group,2-hydroxy-3-chloropropyl group, 1-hydroxymethyl-2-chloroethyl group etc.The C2 to C6 carboxyalkyl group includes a carboxymethyl group,carboxyethyl group, carboxypropyl group, carboxybutyl group,carboxypentyl group etc., and derivatives of the carboxyalkyl group orcarboxy group include a methyl ester compound, ethyl ester compound,acid halide, tosylated compound, mesylated compound, anhydride etc.Preferable examples of E3 include a 2,3-epoxypropyl group, 2-chloroethylgroup, 3-chloropropyl group, 2-hydroxy-3-chloropropyl group,carboxymethyl group, carboxyethyl group, and methyl esters or acidhalides thereof.

The polyoxyalkylenating agents (3p) can be used alone or as a mixture oftwo or more thereof, and the amount used thereof can be regulatedsuitably depending on the amount of the substituent groups (A)introduced into the polysaccharide and a derivative thereof, and usuallythe amount of the polyoxyalkylenating agent used is preferably in therange of 0.0001 to 10 equivalents, particularly 0.00015 to 5equivalents, per constituent monosaccharide residue of thepolysaccharide or a derivative thereof.

This reaction is carried out, as needs arise, preferably in the presenceof an alkali or an acid, and such alkali includes group 1 or 2 elementhydroxides, carbonates, bicarbonates, tertiary amines etc., among whichsodium hydroxide, potassium hydroxide, calcium hydroxide, magnesiumhydroxide and pyridine are preferable. To give an excellent result, theamount of the alkali used is preferably in 1.0- to 10-molar excess, morepreferably 1.05- to 5.0-molar excess, relative to thepolyoxyalkylenating agent (3p) used. The acid includes mineral acids,organic acids etc., among which sulfuric acid, hydrochloric acid,p-toluenesulfonic acid and methanesulfonic acid are preferable. To givean excellent result, the molar ratio of the acid to thepolyoxyalkylenating agent used is preferably in the range of 0.01 to0.5, more preferably 0.1 to 0.3.

The solvent includes lower alcohols such as isopropyl alcohol,tert-butyl alcohol etc. A mixed solvent having preferably 0.1 to 100 wt%, more preferably 1 to 90 wt %, water added to a lower alcohol may beused for the purpose of increasing the reactivity between thepolysaccharide or a derivative thereof and the polyoxyalkylenating agent(3p).

The reaction temperature is preferably in the range of 0 to 150° C.,more preferably 30 to 100° C. After the reaction is finished, thereaction mixture can be neutralized with an acid or alkali. The acidincludes inorganic acids such as sulfuric acid, hydrochloric acid andphosphoric acid and organic acids such as acetic acid, and the alkaliincludes group 1 or 2 element hydroxides such as sodium hydroxide,potassium hydroxide and magnesium hydroxide. The subsequent reaction canalso be carried out without neutralization.

(Sulfonating Reaction)

The sulfonating reaction of the polysaccharide or a derivative thereofis carried out by dissolving or dispersing the polysaccharide or aderivative thereof in a suitable solvent and reacting it with thesulfonating agent (b).

In the sulfonating agent (b), the substituent halogen atom in the C1 toC5 haloalkanesulfonic acid whose hydroxy group may be substitutedincludes a fluorine atom, chlorine atom, bromine atom etc., and saltsthereof include salts with the group 1 or 2 elements such as a sodiumsalt, potassium salt, calcium salt, magnesium salt etc., as well asammonium salts. The sulfonating agent is preferably vinylsulfonic acid,3-halo-2-hydroxypropanesulfonic acid, 3-halopropanesulfonic acid, or2,3-epoxypropanesulfonic acid, and these sulfonating agents can be usedalone or as a mixture of two or more thereof, and the amount of thesulfonating agent used can be suitably regulated depending on a desiredamount of the sulfonic acid groups (B) introduced into thepolysaccharide or a derivative thereof, but is usually preferably in therange of 0 to 10 equivalents, more preferably 0 to 2 equivalents, perconstituent monosaccharide residue of the polysaccharide or a derivativethereof.

Preferably the sulfonating reaction is carried out if necessary in thepresence of an alkali, and such alkali includes group 1 or 2 elementhydroxides, carbonates, bicarbonates etc., among which sodium hydroxide,potassium hydroxide, calcium hydroxide and magnesium hydroxide arepreferable. To give an excellent result, the amount of the alkali usedis preferably in 0.1- to 3.0-molar excess, more preferably 0.5- to1.5-molar excess, relative to the sulfonating agent used.

The solvent includes lower alcohols such as isopropyl alcohol,tert-butyl alcohol etc. A mixed solvent having preferably 0.1 to 90 wt%, more preferably 1 to 50 wt %, water added to a lower alcohol may beused for the purpose of increasing the reactivity between thepolysaccharide or a derivative thereof and the sulfonating agent.

The reaction temperature is preferably in the range of 0 to 150° C.,more preferably 30 to 100° C. After the reaction is finished, the alkalican be neutralized with an acid if necessary. The acid includesinorganic acids such as sulfuric acid, hydrochloric acid and phosphoricacid and organic acids such as acetic acid. Alternatively, thesubsequent reaction can be carried out without neutralization.

(Carboxylation)

The carboxylating reaction of the polysaccharide or a derivative thereofis carried out by dissolving or dispersing the polysaccharide or aderivative thereof in a suitable solvent and reacting it with thecarboxylating agent (c) in the presence of an alkali.

The carboxylating agent (c) is specifically monochloroacetic acid,sodium monochloroacetate, potassium monochloroacetate, sodiummonobromoacetate, potassium monobromoacetate etc. These carboxylatingagents (c) can be used alone or as a mixture of two or more thereof, andthe amount of the carboxylating agent (c) used can be suitably regulateddepending on a desired amount of the carboxyalkyl groups (C) introducedinto the polysaccharide or a derivative thereof, but is usuallypreferably in the range of 0 to 10 equivalents, more preferably 0 to 1equivalent, per constituent monosaccharide residue of the polysaccharideor a derivative thereof.

The alkali used in this reaction includes sodium hydroxide, potassiumhydroxide, calcium hydroxide and magnesium hydroxide. The amount of thealkali used is preferably in 1.0- to 3.0-molar excess, more preferably1.05- to 2.5-molar excess, relative to the carboxylating agent (c) used.An amount of the alkali outside the above range is not preferablebecause when the amount of the alkali is too low, the reaction rate isdecreased, while when the amount is too high, decomposition of thepolysaccharide or a derivative thereof occurs easily.

The solvent includes isopropyl alcohol, tert-butyl alcohol etc. Usually,a mixed solvent having 1 to 90 wt % water added to isopropyl alcohol ortert-butyl alcohol is used for the purpose of increasing the reactivitywith the polysaccharide or a derivative thereof and the carboxylatingagent (c).

The reaction temperature is preferably in the range of 0 to 150° C.,more preferably 30 to 100° C. After the reaction is finished, the alkalican be neutralized with an acid if necessary. The acid includesinorganic acids such as sulfuric acid, hydrochloric acid and phosphoricacid and organic acids such as acetic acid. Alternatively, thesubsequent reaction can be carried out without neutralization.

(Cationizing Reaction)

The cationizing reaction of the polysaccharide or a derivative thereofis carried out by dissolving or dispersing the polysaccharide or aderivative thereof in a suitable solvent and reacting it with thecationizing agent (d).

Among the groups represented by D² in the formula (4p), the C3 to C6epoxylated alkyl group includes a 2,3-epoxypropyl group, 3,4-epoxybutylgroup, 4,5-epoxypentyl group, 5,6-epoxyhexyl group etc. The C1 to C6linear or branched halogenated alkyl group whose hydroxy group may besubstituted includes a 2-chloroethyl group, 3-chloropropyl group,4-chlorobutyl group, 6-chlorohexyl group, 2-bromoethyl group,2-hydroxy-3-chloropropyl group, 1-hydroxymethyl-2-chloroethyl group etc.Preferable examples of D2 include a 2,3-epoxypropyl group, 2-chloroethylgroup, 3-chloropropyl group, 2-hydroxy-3-chloropropyl group etc. Thesecationizing agents (d) can be used alone or as a mixture of two or morethereof, and the amount of the cationizing agent (d) used can beregulated suitably depending on the desired amount of the cationicsubstituent groups (D) introduced into the polysaccharide and aderivative thereof, but is usually preferably in the range of 0 to 10equivalents, particularly 0 to 5 equivalents, per constituentmonosaccharide residue of the polysaccharide or a derivative thereof.

Preferably this reaction is carried out if necessary in the presence ofan alkali, and such alkali includes group 1 or 2 element hydroxides,carbonates, bicarbonates etc., among which sodium hydroxide, potassiumhydroxide, calcium hydroxide, magnesium hydroxide etc. are preferable.To give an excellent result, the amount of the alkali used is preferablyin 1.0- to 3.0-molar excess, more preferably 1.05- to 1.5-molar excess,relative to the cationizing agent (d) used.

The solvent includes lower alcohols such as isopropyl alcohol,tert-butyl alcohol etc. A mixed solvent having preferably 0.1 to 100 wt%, more preferably 1 to 90 wt %, water added to a lower alcohol may beused for the purpose of increasing the reactivity between thepolysaccharide or a derivative thereof and the cationizing agent (d).

The reaction temperature is preferably in the range of 0 to 150° C.,more preferably 30 to 100° C. After the reaction is finished, the alkalican be neutralized with an acid. The acid includes inorganic acids suchas sulfuric acid, hydrochloric acid and phosphoric acid and organicacids such as acetic acid. The subsequent reaction can also be carriedout without neutralization.

When the polysaccharide derivative obtained in the respective reactionsdescribed above is used subsequently in other reaction, the reactionmixture can be used as it is without neutralization, and if necessary,the reaction mixture can be used after separation by filtration or thelike or after washing with hot water, water-containing isopropylalcohol, water-containing acetone etc. to remove the unreacted compound(a), (b), (c) or (d) or salts formed as byproducts by neutralizationetc. When introduction of the objective substituent group is finished,the reaction mixture can be neutralized, separated by filtration etc.and washed if necessary, followed by drying to give the polysaccharidederivative of the present invention.

The thus obtained polysaccharide derivative of the present invention isexcellent in water solubility and useful as an emulsifier having anexcellent emulsifying action to allow a hydrophobic compound to beextremely stably present in water. Accordingly, an aqueous compositioncontaining the polysaccharide derivative of the present invention, whena hydrophobic compound is present, allows the hydrophobic compound to beextremely stably present by the emulsifying, dispersing and protectivecolloidal action of the polysaccharide derivative.

This aqueous polysaccharide derivative composition containing ahydrophobic compound does not undergo a change with time or a change inviscosity or a change in outward appearance such as separation, byadding a generally used surfactant, and releases the hydrophobiccompound efficiently when used, and is thus extremely useful in thetoiletry field. The hydrophobic compound includes higher alcohols,sterols, silicones, fluorine-based oils, oily components etc. to improvethe function and added value of toiletry products.

The content of the polysaccharide derivative in the aqueous compositionis preferably 0.01 to 5 wt %, more preferably 0.05 to 2 wt %. When thehydrophobic compound is added, its amount is preferably 0.0001 to 50 wt%, more preferably 0.001 to 30 wt %.

A surfactant, dispersant, solvent, perfume, dye, inorganic salt and pHadjusting agent used usually in toiletry products can be arbitrarilyadded to the aqueous composition containing the polysaccharidederivative of the present invention.

The polysaccharide derivative of the present invention and an aqueouscomposition containing the same can be used in various toiletry productssuch as a bathing agent, massage cosmetics, a shower agent, a skin careagent, a hair washing agent, a body washing agent, a washing agent forclothing, a finishing agent for clothing and a washing agent for hardsurface.

According to the present invention, allergen on a surface and in spacecan be reduced, and allergen can be particularly efficiently removed.

EXAMPLES

The following examples describe the practice of the present invention.The Examples are mere illustration of the present invention and are notintended to limit the present invention.

Example 1

Compounds A1 to M shown in Table 1 and Aculyn 22 were used to preparesample solutions containing 0.01 wt % Compounds A1 to M and 15 wt %ethanol (special grade, SIGMA), the balance being water. These samplesolutions were examined for the degree of residual activity of miteallergen R by the following QAS method. The results are shown inTable 1. TABLE 1 Sample Degree of residual activity of mite(%) CompoundA1 solution 35 Compound A2 solution 40 Compound B solution 50 Compound Csolution 46 Compound D solution 50 Compound E solution 46 Compound Fsolution 32 Compound G solution 28 Compound H solution 32 Compound Isolution 26 Compound J solution 28 Compound K solution 42 Compound Lsolution 48 Compound M solution 40 Aculyn22(ISP Ltd.) 36 Ion exchangewater 100 15% Aqueous ethanol (standard) 100

wherein X is —OH, —Cl, —OCH₃ or —OC₂H₄.

Compounds A1 to M were obtained by the following synthesis examples.

Aculyn22 is an acrylic acid/alkyl methacrylate/polyoxyethylene (averagenumber of moles added: 20) stearyl ether copolymer available from ISPLtd.

When compound K was dissolved, acetic acid was used as a pH adjustingagent, and the final pH was 5.5. When Aculyn 22 was dissolved, sodiumhydroxide was used as a pH adjusting agent, and the final pH was 8.0.For the other compounds, a pH adjusting agent was not used, and the pHvalues of their solutions were in the range of 7 to 8. These pH valuesare those at 20° C.

Evaluation of Degree of Residual Activity of Mite Allergen by QAS Method

1. An allergen stick of an antigen-specific IgE antibody detectionreagent Qiedel Allergy Screen QAS-IV (FUJI REBIO INC.) is impregnatedwith 100 μl sample solution and left in a moistened box at roomtemperature for 2 hours.

2. The allergen stick is washed for 30 seconds with physiological saline(Ohtsuka Pharmaceutical Co., Ltd.). Thereafter, the allergen stick isimpregnated with 50 μl serum derived from blood of a patient with miteallergy, and then left in a moistened box at room temperature for 18hours thereby reacting antigen-specific IgE antibody in the blood withantigen.

3. The allergen stick is washed for 20 seconds with physiological salineand then the allergen stick is dipped for 30 minutes at room temperaturein a test tube filled with an enzyme-labeled antibody solution(containing 0.0075 mg/mL alkali phosphatase-labeled anti-IgE antibody(mouse), included in QAS kit), to form an antigen/antigen-specific IgEantibody/enzyme-labeled antibody conjugate.

4. The allergen stick is washed with tap water for 2 minutes, and thenthe allergen stick is colored by dipping it for 1 hour at roomtemperature in a test tube filled with a substrate solution (containing2.16 mg/mL 5-bromo-4-chloro-3-indolyl phosphate, attached to QAS kit).

5. The allergen stick is scanned by an image scanner (Sharp JX350), andthe coloration of a Dermatophagoides farinae part and a Dermatophagoidesptemysinus part in an incorporated image is quantified by Lane & SpotAnalyzer (ATTO Corporation). The quantification value shall be regardedto be higher as the color density is increased.

As the negative control stick, an allergen stick impregnated with 15 wt% aqueous ethanol is subjected to the same operation as described above.The coloration of the Dermatophagoides farinae part in the negativecontrol stick is Rt, the coloration of the negative control part is Rr,the coloration of the Dermatophagoides farinae part in the stickimpregnated with the test solution is Dt, and the coloration of thenegative control part is Dr, and (Dt−Dr)/(Rt−Rr)×100 is the degree ofresidual activity of mite allergen Rf (%) for Dermatophagoides farinaeallergen. Similarly, the Dermatophagoides ptemysinus part is alsoexamined to determine the degree of residual activity of mite allergenRp (%) for Dermatophagoides ptemysinus allergen by the same calculation.The mean value of Rf and Rp is regarded as the degree of residualactivity of mite allergen R (%).

Example 2

Space with a floor area of 7.4 m² and a height of 2.3 m (capacity 17 m²,temperature 23° C.) was sealed, and a cotton futon actually used for 2years in home was given with an impact for 10 seconds with a futonbeater to generate dust in the space and stir up the dust. Then, 17 g ofthe allergen-reducing agent in Table 2 was sprayed into the space upwardat a direction of 45° from a height of 1.7 meters over the floor byusing a trigger-type spray (trigger attached to ALERUCLEAN CleaningSpray for futon, manufactured by Kao Corporation).

Thirty minutes after spraying, a high-volume air sampler (HV-500F,Shibata Scientific Technology Ltd.) equipped with a glass fiber filter(GB-100R-110A, Shibata Scientific Technology Ltd.) was operated underthe condition of 500 L/min. for 60 minutes on the floor, to capture duston the filter. The glass fiber filter on which the dust had beencaptured was squeezed in 1 cc or less solution containing PBS (phosphatebuffer solution, pH 7.4±0.1 (that is, a solution of 0.144 g/L KH₂PO₄,9.00 g/L NaCl and 0.795 g/L Na₂HPO₄.7H₂O in distilled water, containing0.05 wt % Tween 20 (SIGMA), hereinafter, referred to as T-PBS) toextract allergen from the dust, and the concentration of Der f II in theextract was colored by sandwich ELISA.

Coloration without spraying was compared with coloration with sprayingto evaluate the effect of the spraying on reduction of allergen.

A test without spraying and a test of each allergen-reducing agent inTable 2 were carried out one after another and repeated 4 times in asuitable different order, and when the allergen reducing effectsexamined 4 times were compared, all of the allergen-reducing agents inthe formulation examples in Table 2 exhibited an excellent allergenreducing effect. Formulation Examples 3 to 5 and Formulation Examples 10to 15 gave a particularly excellent reducing effect. The results of allthe formulation examples were superior to those of the tests carried outseparately by spraying water only.

Example 3

Space with a floor area of 7.4 m² and a height of 2.3 m (capacity 17 m²,temperature 23° C.) was sealed, and a cotton futon actually used for 2years in home was given with an impact for 10 seconds with a futonbeater to generate dust in the space and stir up the dust.

After 3 hours, the floor surface was cleaned at 20 seconds/m² with avacuum-cleaner (CV-CD4, suction power of 530 W, manufactured by Hitachi,Ltd.). Immediately thereafter, a sheet structure A wherein a nonwovenfabric obtained by a method of preparing a nonwoven fabric as shownbelow was impregnated at an impregnation degree of 250% (ratio byweight) with the allergen-reducing agent in Table 2 was fitted inQuickle Wiper (Kao Corporation) and used to wipe the floor surface.

After wiping, the floor surface was left for 3 hours and then wiped thewhole floor surface with a wiping sheet B having a commercial cleaningsheet (Floor Quickle Dry Type, Kao Corporation) impregnated at animpregnation degree of 150% (ratio by weight) with T-PBS.

From the sheet B, the contaminated PBS was squeezed out and colored bysandwich ELISA shown below.

The coloration in a test (control test) of sheet A impregnated withwater in place of the allergen-reducing agent in Table 2 was comparedwith the coloration of sheet A impregnated with the composition shown inTable 2, to evaluate the effect of reducing allergen.

The control test and the test of the allergen-reducing agent in Table 2were carried out one after another and repeated 4 times in a suitabledifferent order, and when the effects of the allergen reducing effectexamined 4 times were compared, all of the allergen-reducing agents inthe formulation examples in Table 2 exhibited an allergen reducingeffect superior to that of the control test. Formulation Examples 3 to 5and Formulation Examples 10 to 15 gave a particularly excellent reducingeffect.

Example 4

Space with a floor area of 7.4 m² and a height of 2.3 m (capacity 17 m²,temperature 23° C.) was sealed, and a cotton futon actually used for 2years in home was given with an impact for 10 seconds with a futonbeater to generate dust in the space and stir up the dust.

After 3 hours, a sheet structure A wherein a nonwoven fabric obtained bya method of preparing a nonwoven fabric as shown below was impregnatedat an impregnation degree of 250% (ratio by weight) with theallergen-reducing agent in Table 2 was fitted in a wiper device (QuickleWiper, Kao Corporation) and used to wipe the floor surface. Immediatelythereafter, the floor surface was cleaned at 20 seconds/m² with avacuum-cleaner (CV-CD4, suction power of 530 W, Hitachi, Ltd.).

After wiping, the floor surface was left and then wiped the whole floorsurface with a wiping sheet B having a commercial cleaning sheet (FloorQuickle Dry Type, Kao Corporation) impregnated at an impregnation degreeof 150% (ratio by weight) with T-PBS.

From the sheet B, the contaminated PBS was squeezed out and colored bysandwich ELISA shown below.

The coloration in a test (control test) of the sheet impregnated withwater in place of the allergen-reducing agent in Table 2 was comparedwith the coloration of the sheet impregnated with the allergen-reducingagent shown in Table 2, to evaluate the effect of reducing allergen.

The control test and the test of the allergen-reducing agent in Table 2were carried out one after another and repeated 4 times in a suitabledifferent order, and when the effects of the allergen reducing effectexamined 4 times were compared, all of the allergen-reducing agents inthe formulation examples in Table 2 exhibited an excellent allergenreducing effect. Formulation Examples 3 to 5 and Formulation Examples 10to 15 gave a particularly excellent reducing effect.

The reducing degrees were higher than those in Example 3 where thecorresponding formulations were used.

Example 5

Space with a floor area of 7.4 m² and a height of 2.3 m (capacity 17 m²,temperature 23° C.) was sealed, and a cotton futon actually used for 2years in home was given with an impact for 10 seconds with a futonbeater to generate dust in the space and stir up the dust.

After 3 hours, 30 g of the allergen-reducing agent in Table 2 wassprayed into space downward at a direction of 45° from a height of 0.6 mover the floor by using a trigger-type spray (trigger attached toALERUCLEAN Cleaning Spray for futon, manufactured by Kao Corporation).Immediately thereafter, 4 nonwoven fabrics obtained by a method ofpreparing a nonwoven fabric as shown below, which were fitted in QuickleWiper (Kao Corporation), were used one after another to clean the floorsurface.

After 3 hours, the floor surface was wiped with a wiping sheet B havinga commercial cleaning sheet (Floor Quickle Dry Type, Kao Corporation)impregnated at an impregnation degree of 150% (ratio by weight) withT-PBS.

From the sheet B, the contaminated PBS was squeezed out and colored bysandwich ELISA shown below.

The coloration in a test (control test) by spraying water in place ofthe allergen-reducing agent in Table 2 was compared with the colorationin a test by spraying the allergen-reducing agent shown in Table 2, toevaluate the effect of reducing allergen.

The control test and the test of the allergen-reducing agent in Table 2were carried out one after another and repeated 4 times in a suitabledifferent order, and when the effects of the allergen reducing effectexamined 4 times were compared, all of the allergen-reducing agents inthe formulation examples in Table 2 exhibited a more excellent allergenreducing effect. Formulation Examples 3 to 5 and Formulation Examples 10to 15 gave a particularly excellent reducing effect.

<Sandwich ELISA Method>

1. Monoclonal antibody 15E11 (Seikagaku Corporation) is diluted at aconcentration of 2 μg/ml in PBS (phosphate buffer solution, pH 7.4±0.1(that is, a solution of 0.144 g/L KH₂PO₄, 9.00 g/L NaCl and 0.795 g/LNa₂HPO₄.7H₂O in distilled water), then pipetted into a well (50 μl/well)of a microplate (ELISA PLATE H TYPE, Sumitomo Bakelite Co., Ltd.) andleft at room temperature for 2 hours.

2. The plate is washed 3 times with PBS.

3. PBS (Block Ace, Dainippon Pharmaceutical Co., Ltd.) containing 1% BSA(SIGMA) is pipetted into each well (200 μl/well) and left at roomtemperature for 1 hour for blocking.

4. The plate is washed 3 times with T-PBS (PBS containing 0.05 wt %Tween 20 (SIGMA)).

5. Separately, 0.3 μg/ml rDer f II (Seikagaku Corporation) is diluted2^(n)-fold with 9-tube T-PBS, and each dilution is pipetted as astandard in a volume of 50 μl into each well, while a well to which 50μl T-PBS is added as a negative control in place of rDer f II isprepared. The sample to be measured is diluted suitably with T-PBS andpipetted in a volume of 50 μl into each well. The plate is left at roomtemperature for 2 hours.

6. The plate is washed 3 times with T-PBS.

7. HRP-labeled 13A4 (Seikagaku Corporation) at optimum concentration ispipetted in a volume of 50 μl into each well and left at roomtemperature for 2 hours.

8. The plate is washed 3 times with T-PBS.

9. A coloration kit T for peroxidase (Sumitomo Bakelite Co., Ltd.) isused in coloration. First, 0.1 ml substrate solution is added to andmixed with 10 mL coloration agent to form a coloration solution. Thiscoloration solution is pipetted in a volume of 100 μl into each well andcolored at room temperature. According to this method, higher yellowcoloration is indicative of a higher concentration of allergen in thesolution.

<Method of Preparing a Nonwoven Fabric>

An air-through nonwoven fabric with a basis weight of 27 g/m² wasprepared from low-melting fibers having a core/sheath structure (2.8dtex×51 mm; the melting point of the sheath component, 130° C.) in acubic crimped form wherein the core was made of polypropylene and thesheath was made of polyethylene. The fibers were heat-bonded to oneanother at a temperature of 140° C. The breaking strength of theair-through nonwoven fabric was 1660 cN/25 mm in the machine direction(MD) and 220 cN/25 mm in the crosswise direction (CD).

Separately, rayon fibers (1.7 dtex×40 mm), acrylic fibers (0.9 dtex×51mm), and core/sheath fibers (1.0 dtex×38 mm), having polypropylene asthe core and polyethylene as the sheath, were mixed at a ratio of50/25/25 by weight. A fiber web having a basis weight of 19 g/m2 wasprepared with a card machine, using an ordinary method. The air-throughnonwoven fabric was sandwiched between the fiber webs thus obtained. Theresulting product was subjected to water needling under low-energyconditions, and the air-through nonwoven fabric and the fiber webs wereinterweaved with one another to prepare a composite spunlace nonwovenfabric with a basis weight of 65 g/m² having a surface layer with highfreedom of fibers. Using an ultrasonic embossing machine, the wholesurface of the prepared nonwoven fabric was embossed to have an embosseddiamond pattern to obtain the nonwoven fabric used in the Examplesdescribed above. TABLE 2 Formulation example 1 2 3 4 5 6 7 8 AllergenCompounding (a) Compound A1 0.1 0.1 0.1 reducing ingredients Compound A20.1 0.2 0.1 agent (wt %) Compound B 0.1 0.1 Compound C 0.1 Compound D0.1 Compound E Compound F Compound G Compound H Compound I Compound JAquiline 22(ISP Ltd.) (b) Water Balance Balance Balance Balance BalanceBalance Balance Balance (c) Ethanol 3.0 5.0 5.0 3.0 2.0 5.0 5.0 5.0Isopropanol 1.0 2.0 (d) Dihydrojasmone 0.05 0.05 0.05 Methyldihydrojasmonate 0.05 0.05 0.05 0.05 0.05 0.05 0.05 (e) Benzalkoniumchloride 0.01 0.01 Polylysine 0.02 0.02 0.02 Sodium sulfate 0.2 0.2 0.2Propyleneglycol 1.0 1.0 1.0 monomethyl ether Total 100 100 100 100 100100 100 100 pH(20° C.) 7 7 7 7 7 7 7 7 Formulation example 9 10 11 12 1314 15 Allergen Compounding (a) Compound A1 reducing ingredients CompoundA2 agent (wt %) Compound B Compound C Compound D Compound E 0.1 CompoundF 0.1 Compound G 0.1 Compound H 0.1 Compound I 0.1 Compound J 0.1Aquiline 22(ISP Ltd.) 0.1 (b) Water Balance Balance Balance BalanceBalance Balance Balance (c) Ethanol 5.0 5.0 5.0 5.0 5.0 5.0 5.0Isopropanol (d) Dihydrojasmone Methyl dihydrojasmonate 0.05 0.05 (e)Benzalkonium chloride Polylysine Sodium sulfate Propyleneglycolmonomethyl ether Total 100 100 100 100 100 100 100 pH(20° C.) 7 7 7 7 77 7

Compounds A1, A2, B, C, D, E, F, G, H, I and J in Table 2 were obtainedby the Synthesis Examples below. Aculyn 22 is a polymer compound fromISP Ltd., that is, an acrylic acid/alkyl methacrylate/polyoxyethylene(average number of moles added: 20) stearyl ether copolymer. In thetable, the pH value was regulated by using sulfuric acid and aminomethylpropanol as the pH adjusting agent.

Synthesis Example 1 Compound A1

80 g of hydroxyethyl cellulose (HEC-QP100MH, manufactured by UnionCarbide) having a weight-average molecular weight of 1,500,000 and ahydroxyethyl group substitution degree of 1.8, 640 g of 80% aqueousisopropyl alcohol (IPA) and 5.34 g of 48% aqueous sodium hydroxidesolution were mixed to prepare slurry and stirred at room temperaturefor 30 minutes in a nitrogen atmosphere. To this solution was added to12.78 g polyoxyalkylene compound represented by the following formula:

The mixture was reacted at 80° C. for 8 hours for polyoxyalkylenation.After the reaction was finished, the reaction solution was neutralizedwith acetic acid, and the reaction product was separated by filtration.The reaction product washed twice with 500 g isopropyl alcohol and driedat 60° C. under reduced pressure for 1 day to give 72 g compound A1. Thedegree of substitution of the polyoxyalkylene group was 0.004.

Synthesis Example 2 Compound A2

According to methods described in Synthesis Example 1 and WO00/73351,hydroxyethyl cellulose having a weight-average molecular weight of200,000 and a hydroxyethyl group substitution degree of 2.5(manufactured by Hercules Incorporated) was used, and a polyoxyalkylenecompound represented by the following formula was added thereto to givecompound A2 having a polyoxyalkylene group substitution degree of 0.014.

Synthesis Example 3 Compound B

20 g polyvinyl alcohol having an average polymerization degree of 2000,200 g dimethyl sulfoxide (DMSO), and 1.81 g granular NaOH were mixed andstirred at 70° C. When the solution became uniform, it was cooled. 1.87g compound represented by the following formula:

was added at room temperature. The mixture was aged at 80° C. for 8hours. After cooling, the reaction solution was neutralized with 2.59 mLacetic acid. The reaction product was added to IPA. Precipitated whitesolids were filtered and the resulting solids were washed with IPA (300mL×3). After drying under reduced pressure, 19.0 g compound B having thefollowing unit shown below was obtained.

The degree of substitution of the substituent group including thepolyoxyalkylene group in the resulting compound B was 0.0033.

Synthesis Example 4 Compound C

97.1 g monomer A and 20.7 g monomer B in the above scheme and 180 gethanol were mixed. The reaction system was degassed by blowing anitrogen gas into the solution (20 mL/min., 1 hour) and then heated to60° C. Thereafter, 82.8 g solution of V-65 (azo polymerizationinitiator, Wako Pure Chemical Industries, Ltd.) in ethanol (3 wt %) wasadded dropwise to it while the temperature was kept at 66° C. Afterdropping, the mixture was aged at 60° C. for 12 hours. After thereaction was finished, the resulting reaction product was added dropwiseto 2 kg diisopropyl ether. The resulting white solids were separated byfiltration and washed with diisopropyl ether (500 g×twice). After dryingunder reduced pressure, 105 g compound C was obtained. The degree ofintroduction of the monomer B in the resulting compound C, as determinedby NMR, was 0.025. The weight-average molecular weight was 51000.

Synthesis Example 5 Compound D

501.8 g monomer C and 20.7 g monomer B in the above scheme and 780 gethanol were mixed. The reaction system was degassed by blowing anitrogen gas into the solution (40 mL/min., 1 hour) and then heated to60° C. Thereafter, 82.8 g V-65 ethanol solution (3 wt %) was dropped toit while the temperature was kept at 60° C. After dropping, the mixturewas aged at 60° C. for 12 hours. After the reaction was finished, theresulting reaction product was added dropwise to 5 kg diisopropyl ether.The resulting white solids were separated by filtration and washed withdiisopropyl ether (500 g×twice). After drying under reduced pressure,490 g compound D was obtained. The degree of introduction of the monomerB in the resulting compound D, as determined by NMR, was 0.022. Theweight-average molecular weight was 110000.

Synthesis Example 6 Compound E

3 g polyglycidol having a weight-average molecular weight of 5400, 100 gDMSO, and 0.16 g granular NaOH were mixed and stirred at 70° C. When thesolution became uniform, it was cooled. 0.765 g compound represented bythe following formula:

was added thereto at room temperature, and the mixture was aged at 80°C. for 8 hours. After cooling, the reaction solution was neutralizedwith 0.23 mL acetic acid. DMSO was distilled away, and the resultingpale yellow viscous solid washed with IPA (30 mL×3). After drying underreduced pressure, 2.9 g compound E having the unit shown below wasobtained.

The degree of substitution of the substituent group including thepolyoxyalkylene group in the resulting compound E was 0.0053.

Synthesis Example 7 (Compound F) HEC (200,000)+EO-Cholesteryl (Degree ofSubstitution 3.3/1000))

50 g hydroxyethyl cellulose having a weight-average molecular weight ofabout 200,000 (Natrozol 250G, manufactured by Hercules Incorporated),225 g isopropyl alcohol and 40 g ion exchange water were mixed andstirred at room temperature for 1 hour in a nitrogen stream. 5.59 gcompound (F′) and 3.06 g of 48% aqueous NaOH were added to the solutionand heated to 80° C. Thereafter, the mixture was aged at 80° C. for 8hours. After aging was finished, the reaction solution was cooled toroom temperature and neutralized with acetic acid. The reaction mixturewas filtered, and the resulting solids were washed twice with 400 gisopropyl alcohol. The resulting reaction product was dried for 1 dayunder reduced pressure to give 48 g polysaccharide derivative (compoundF). The degree of substitution of the cholesteryl group of the resultingpolysaccharide derivative was 0.0033.

Synthesis Example 8 (Compound G) HEC (100,000)+EO-Branched Alkyl (Degreeof Substitution 7.1/1000))

50 g hydroxyethyl cellulose having a weight-average molecular weight ofabout 100,000 (Natrozol 250LR, manufactured by Hercules Incorporated),225 g isopropyl alcohol and 25 g ion exchange water were mixed andstirred at room temperature for 1 hour in a nitrogen stream. 8.08 gcompound (G′) and 3.06 g of 48% aqueous NaOH were added to the solutionand heated to 80° C. Thereafter, the mixture was aged at 80° C. for 9hours. After aging was finished, the reaction solution was cooled toroom temperature and neutralized with acetic acid. The reaction mixturewas filtered, and the resulting solids were washed twice with 400 gisopropyl alcohol. The resulting reaction product was dried for 1 dayunder reduced pressure to give 45 g polysaccharide derivative (compoundG). The degree of substitution of the octyldodecyl group of theresulting polysaccharide derivative was 0.0071.

Synthesis Example 9 (Compound H) HEC (200,000)+EO-Branched Alkyl (Degreeof Substitution 8.6/1000))

50 g hydroxyethyl cellulose having a weight-average molecular weight ofabout 200,000 (Natrozol 250G, manufactured by Hercules Incorporated),225 g isopropyl alcohol and 40 g ion exchange water were mixed andstirred at room temperature for 1 hour in a nitrogen stream. 7.89 gcompound (H′) and 3.06 g of 48% aqueous NaOH were added to the solutionand heated to 80° C. Thereafter, the mixture was aged at 80° C. for 8hours. After aging was finished, the reaction solution was cooled toroom temperature and neutralized with acetic acid. The reaction mixturewas filtered, and the resulting solids were washed twice with 400 gisopropyl alcohol. The resulting reaction product was dried for 1 dayunder reduced pressure to give 47 g polysaccharide derivative (compoundH). The degree of substitution of the isostearyl group of the resultingpolysaccharide derivative was 0.0086.

Synthesis Example 10 (Compound I) HEC (200,000)+EO-Unsaturated Alkyl(Degree of Substitution 8.1/1000))

40 g hydroxyethyl cellulose having a weight-average molecular weight ofabout 200,000 (Natrozol 250G, manufactured by Hercules Incorporated),180 g isopropyl alcohol and 32 g ion exchange water were mixed andstirred at room temperature for 1 hour in a nitrogen stream. 4.52 gcompound (1′) and 2.45 g of 48% aqueous NaOH were added to the solutionand heated to 80° C. Thereafter, the mixture was aged at 80° C. for 8hours. After aging was finished, the reaction solution was cooled toroom temperature and neutralized with acetic acid. The reaction mixturewas filtered, and the resulting solids were washed twice with 400 gisopropyl alcohol. The resulting reaction product was dried for 1 dayunder reduced pressure to give 38 g polysaccharide derivative (compoundI). The degree of substitution of the oleyl group of the resultingpolysaccharide derivative was 0.0081.

Synthesis Example 11 (Compound J) Inulin+EO-Lauryl (Degree ofSubstitution 26.6/1000))

50 g inulin (FujiFF, Fuji nihon seito Corporation), 60 g isopropylalcohol and 140 g ion exchange water were mixed and stirred at roomtemperature for 1 hour in a nitrogen stream. 40.8 g compound (J′) and5.14 g of 48% aqueous NaOH were added to the solution and heated to 80°C. Thereafter, the mixture was aged at 80° C. for 8 hours. After agingwas finished, the reaction solution was cooled to room temperature andneutralized with acetic acid. The reaction product was added graduallyto 2000 g of acetone. The precipitated solids were filtered, and theresulting solids were washed twice with 400 g acetone. The resultingreaction product was dried for 1 day under reduced pressure to give 51 gpolysaccharide derivative (compound J). The degree of substitution ofthe lauryl group of the resulting polysaccharide derivative was 0.0266.

Synthesis Example 12 (Compound K) Chitosan (50,000)+EO-Lauryl (Degree ofSubstitution 13/1000))

30 g chitosan 10 (manufactured by Wako Pure Chemical Industries, Ltd.),45 g isopropyl alcohol and 105 g ion exchange water were mixed andstirred at room temperature for 1 hour in a nitrogen stream. 11.84 gcompound (K′) was added to the solution and heated to 80° C. Thereafter,the mixture was aged at 80° C. for 8 hours. After aging was finished,the reaction solution was cooled to room temperature and neutralizedwith acetic acid. The resulting reaction mixture was filtered, and theresulting solids were washed twice with 300 g isopropyl alcohol. Theresulting reaction product was dried for 1 day under reduced pressure togive 31 g polysaccharide derivative (compound K). The degree ofsubstitution of the lauryl group of the resulting polysaccharidederivative was 0.013.

Synthesis Example 13 (Compound L) Cluster Dextrin+EO-Lauryl (Degree ofSubstitution 2.4/1000))

40 g cluster dextrin (manufactured by Nihon Shokuhin Kako Co., Ltd.), 72g isopropyl alcohol and 168 g ion exchange water were mixed and stirredat room temperature for 1 hour in a nitrogen stream. 6.53 g compound(L′) and 4.11 g of 48% aqueous NaOH were added to the solution andheated to 80° C. Thereafter, the mixture was aged at 80° C. for 8 hours.After aging was finished, the reaction solution was cooled to roomtemperature and neutralized with acetic acid. The resulting reactionmixture was added gradually to 2000 g acetone. The precipitated solidswere filtered, and the resulting solids were washed twice with 400 gisopropyl alcohol. The resulting reaction product was dried for 1 dayunder reduced pressure to give 39 g polysaccharide derivative (compoundL). The degree of substitution of the lauryl group of the resultingpolysaccharide derivative was 0.024.

Synthesis Example 14 (Compound M) Guar Gum (50,000)+EO-Lauryl (Degree ofSubstitution 3.8/1000))

40 g guar gum having a weight-average molecular weight of about 50,000(MEYPRO-GUM manufactured by Sansho Co., Ltd.), 40 g isopropyl alcoholand 160 g ion exchange water were mixed and stirred at room temperaturefor 1 hour in a nitrogen stream. 19.73 g compound (M′) and 3.72 g of 48%aqueous NaOH were added to the solution and heated to 80° C. Thereafter,the mixture was aged at 80° C. for 8 hours. After aging was finished,the reaction solution was cooled to room temperature and neutralizedwith acetic acid. The resulting reaction mixture was filtered, and theresulting solids were washed twice with 400 g isopropyl alcohol. Theresulting reaction product was dried for 1 day under reduced pressure togive 32 g polysaccharide derivative (compound M). The degree ofsubstitution of the lauryl group of the resulting polysaccharidederivative was 0.0038.

In Synthesis Examples 15 and 20 below, the degree of substitution of thesubstituent group (A) in the polysaccharide derivative of the presentinvention was determined according to the Zeisel method (D. G. Anderson,Anal. Chem., 43, 894 (1971)), and the degrees of substitution of thesulfoalkyl group (B), the carboxyalkyl group (C) and the cationicsubstituent group (D) were determined by the colloid titration method.In the following examples, the “degree of substitution” refers to theaverage number of substituent groups per constituent monosaccharideresidue.

Synthesis Example 15

50 g hydroxyethyl cellulose (Natrozol 250LR having a weight-averagemolecular weight of about 100,000, manufactured by HerculesIncorporated), 225 g isopropyl alcohol and 25 g ion exchange water weremixed and stirred at room temperature for 1 hour in a nitrogen stream.8.4 g compound (1′) and 3.06 g of 48% aqueous NaOH were added to thesolution and stirred for 20 minutes in a nitrogen stream at roomtemperature. Thereafter, the mixture was heated to 80° C. and reactedfor 8 hours. After the reaction was finished, the reaction mixture wascooled to room temperature and neutralized with acetic acid. Thereaction mixture was filtered, and the resulting solids were washedtwice with 400 g isopropyl alcohol, and the resulting product was driedfor 1 day at 60° C. under reduced pressure to give 45 g cellulosederivative having a polyoxyethylene cholesteryl ether group introducedinto it. The degree of substitution of the cholesteryl group of theresulting cellulose derivative was 0.0061.

Synthesis Example 16

40 g hydroxyethyl cellulose (Natrozol 250M having a weight-averagemolecular weight of about 500,000, manufactured by HerculesIncorporated), 260 g isopropyl alcohol and 64 g ion exchange water weremixed and stirred at room temperature for 1 hour in a nitrogen stream.9.3 g compound (2′) and 2.45 g of 48% aqueous NaOH were added to thesolution and stirred for 20 minutes in a nitrogen stream at roomtemperature. Thereafter, the mixture was heated to 80° C. and reactedfor 8 hours. After the reaction was finished, the reaction mixture wascooled to room temperature and neutralized with acetic acid. Thereaction mixture was filtered, and the resulting solids were washedtwice with 400 g isopropyl alcohol, and the resulting product was driedfor 1 day at 60° C. under reduced pressure to give 49 g cellulosederivative having a polyoxyethylene cholesteryl ether group introducedinto it. The degree of substitution of the cholesteryl group of theresulting cellulose derivative was 0.0025.

Synthesis Example 17

40 g hydroxyethyl cellulose (Natrozol 250HHX having a weight-averagemolecular weight of about 1,500,000, manufactured by HerculesIncorporated), 260 g isopropyl alcohol and 64 g ion exchange water weremixed and stirred at room temperature for 1 hour in a nitrogen stream.3.6 g compound (3′) and 2.45 g of 48% aqueous NaOH were added to thesolution and stirred for 20 minutes in a nitrogen stream at roomtemperature. Thereafter, the mixture was heated to 80° C. and reachedfor 8 hours. After the reaction was finished, the reaction mixture wascooled to room temperature and neutralized with acetic acid. Thereaction mixture was filtered, and the resulting solids were washedtwice with 400 g isopropyl alcohol, and the resulting product was driedfor 1 day at 60° C. under reduced pressure to give 46 g cellulosederivative having a polyoxyethylene cholesteryl ether group introducedinto it. The degree of substitution of the cholesteryl group of theresulting cellulose derivative was 0.0031.

Synthesis Example 18

80 g potato starch (manufactured by Katayama Chemical Inc.), 320 gisopropyl alcohol and 320 g ion exchange water were mixed and stirred atroom temperature for 1 hour in a nitrogen stream. 14.0 g compound (2′)and 5.5 g of 48% aqueous NaOH were added to the solution and stirred for20 minutes in a nitrogen stream at room temperature. Thereafter, themixture was heated to 80° C. and reacted for 8 hours. After the reactionwas finished, the reaction mixture was cooled to room temperature andneutralized with acetic acid. The reaction mixture was filtered, and theresulting solids were washed twice with 400 g isopropyl alcohol, and theresulting product was dried for 1 day at 60° C. under reduced pressureto give 76 g starch derivative having a polyoxyethylene cholesterylether group introduced into it. The degree of substitution of thepolyoxycholesteryl group of the resulting starch derivative was 0.0045.

30 g of the resulting starch derivative, 75 g isopropyl alcohol and 75 gion exchange water were mixed and stirred at room temperature for 1 hourin a nitrogen stream. 4.33 g sodium 3-chloro-2-hydroxypropanesulfonateand 3.67 g of 48% aqueous NaOH were added to the solution and stirredfor 3 hours at 50° C. After stirring was finished, the reaction mixturewas cooled to room temperature and neutralized with acetic acid. Thereaction product was separated by filtration, and the resulting reactionproduct washed twice with 180 g of 50% isopropyl alcohol and twice with200 g of isopropyl alcohol. The resulting cake was dried for 1 day underreduced pressure to give 28 g starch derivative having a polyoxyethylenecholesteryl ether group and a sulfonate group introduced into it. Thedegrees of substitution of the cholesteryl group and sulfonate group ofthe resulting starch derivative were 0.0045 and 0.11, respectively.

Synthesis Example 19

40 g hydroxyethyl cellulose (Natrozol 250M having a weight-averagemolecular weight of about 500,000, manufactured by HerculesIncorporated), 260 g isopropyl alcohol and 64 g ion exchange water weremixed and stirred at room temperature for 1 hour in a nitrogen stream.11.2 g compound (1′) and 2.45 g of 48% aqueous NaOH were added to thesolution and stirred for 20 minutes in a nitrogen stream at roomtemperature. Thereafter, the mixture was heated to 80° C. and reactedfor 8 hours. After the reaction was finished, the reaction mixture wascooled to room temperature and neutralized with acetic acid. Thereaction mixture was filtered, and the resulting solids were washedtwice with 400 g isopropyl alcohol, and the resulting product was driedfor 1 day at 60° C. under reduced pressure to give 48 g cellulosederivative having a polyoxyethylene cholesteryl ether group introducedinto it. The degree of substitution of the polyoxycholesteryl group ofthe resulting cellulose derivative was 0.0053.

30 g of the resulting cellulose derivative, 147 g isopropyl alcohol and63 g ion exchange water were mixed and stirred at room temperature for 1hour in a nitrogen stream. 4.154 g (3-chloro-2-hydroxy-n-propyl)trimethyl ammonium chloride and 3.67 g of 48% aqueous NaOH were added tothe solution and stirred for 3 hours at 50° C. After stirring wasfinished, the reaction mixture was cooled to room temperature andneutralized with acetic acid. The reaction product was separated byfiltration, and the resulting reaction product washed twice with 180 gof 70% isopropyl alcohol. The resulting cake was dried for 1 day underreduced pressure to give 30 g cellulose derivative having apolyoxyethylene cholesteryl ether group and a cation group introducedinto it. The degrees of substitution of the cholesteryl group and cationgroup of the resulting cellulose derivative were 0.0053 and 0.13,respectively.

Synthesis Example 20

40 g hydroxyethyl cellulose (Natrozol 250M having a weight-averagemolecular weight of about 500,000, manufactured by HerculesIncorporated), 260 g isopropyl alcohol and 64 g ion exchange water weremixed and stirred at room temperature for 1 hour in a nitrogen stream.11.2 g compound (1′) and 2.45 g of 48% aqueous NaOH were added to thesolution and stirred for 20 minutes in a nitrogen stream at roomtemperature. Thereafter, the mixture was heated to 80° C. and reactedfor 8 hours. After the reaction was finished, the reaction mixture wascooled to room temperature and neutralized with acetic acid. Thereaction mixture was filtered, and the resulting solids were washedtwice with 400 g isopropyl alcohol, and the resulting product was driedfor 1 day at 60° C. under reduced pressure to give 48 g cellulosederivative having a polyoxyethylene cholesteryl ether group introducedinto it.

30 g of the resulting cellulose derivative, 147 g isopropyl alcohol and63 g ion exchange water were mixed and stirred at room temperature for 1hour in a nitrogen stream. 2.56 g sodium chloroacetate and 3.67 g of 48%aqueous NaOH were added to the solution and stirred for 3 hours at 50°C. After stirring was finished, the reaction mixture was cooled to roomtemperature and neutralized with acetic acid. The reaction product wasseparated by filtration, and the resulting reaction product washed twicewith 180 g of 70% isopropyl alcohol and twice with 200 g isopropylalcohol. The resulting cake was dried for 1 day under reduced pressureto give 30 g polyoxycholesterylated and carboxymethylated cellulosederivative. The degrees of substitution of the cholesteryl group andcation group of the resulting cellulose derivative were 0.0053 and 0.14,respectively.

1. An allergen-reducing agent comprising water and a water-solublepolymer compound having units having hydroxy or carboxy groups whereinat least a part of hydrogen atoms of the hydroxy or carboxy groups aresubstituted by groups represented by the following formula (1):—R^(1a)—(OR^(1b))_(p)-A-R^(1c)  (1) wherein R^(1a) is a C1 to C6alkylene group which may be substituted with a hydroxy or oxo group,R^(1b) is a C1 to C6 alkylene group, R^(1c) is a group selected from thegroup consisting of a C4 to C30 hydrocarbon group which may besubstituted with a hydroxy group, a C1 to C5 sulfoalkyl group which maybe substituted with a hydroxy group, and a hydrocarbon group which has asteroid skeleton, A is a group selected from the group consisting of—O—, —OCO— and —COO—, p is 0 to 50 (average number of moles added), and(OR^(1b)) moles whose number is p may be the same or different.
 2. Theallergen-reducing agent according to claim 1, wherein the water-solublecompound comprises monomer units (a1) and (a2) represented by thefollowing formulae (2) and (3), respectively, a molar ratio of (a1)/(a2)is 1/1500 to 30/100 and a ratio of (a1) and (a2) in total in themolecule is 50 to 100 mol %:

wherein R^(2a) is a hydrogen atom or a C1 to C3 alkyl group, R^(2b) is agroup selected from a hydrogen atom and —COOM, M being a hydrogen atom,an alkali metal atom or an alkaline earth metal atom, R^(2c) is a groupselected from a hydrogen atom, a C1 to C3 alkyl group and a hydroxygroup, R^(2d) is a C1 to C6 alkylene group which may be substituted witha hydroxy group, R^(2e) is a C1 to C6 alkylene group, R^(2f) is a C4 toC30 hydrocarbon group which may be substituted with a hydroxy group, Bis a group selected from —O—, —COO—, —OCO— and —CONR^(2g) —, R^(2g)being a hydrogen atom, a C1 to C3 alkyl group or a C1 to C3 hydroxyalkylgroup, E is a group selected from —O—, —OCO— and —COO—, q is 0 to 50(average number of moles added), and (OR^(2e)) moles whose number is qmay be the same or different;

wherein R^(3a) is a hydrogen atom or a C1 to C3 alkyl group, R^(3b) is agroup selected from a hydrogen atom and —COOM, M being a hydrogen atom,an alkali metal atom or an alkaline earth metal atom, R^(3c) is a groupselected from a hydrogen atom, a C1 to C3 alkyl group and a hydroxygroup, G is —COOM, —OH, -T-(R^(3d)O)_(c)—H, —CON(R^(3e))(R^(3f)),—COO—R^(3g)—N⁺(R^(3h))(R^(3i))(R^(3j)).X⁻,—COO—R^(3g)—N(R^(3h))(R^(3j)),—CON(R^(3e))—R^(3g)—N⁺(R^(3h))(R^(3i))(R^(3j)).X⁻,—CON(R^(3e))—R^(3g)—N(R^(3h))(R^(3j)) or a 5- or 6-memberredheterocyclic group having at least one amino or amide group in the ring,M is a hydrogen atom, an alkali metal atom or an alkaline earth metalatom, T is a group selected from —O— and —COO—, R^(3d) is a C1 to C6alkylene group, R^(3e), R^(3f), R^(3h), R^(3i) and R^(3j) each representa hydrogen atom, a C1 to C3 alkyl group or a C1 to C3 hydroxyalkylgroup, R^(3g) is a C1 to C5 alkylene group, X⁻ represents an organic orinorganic anionic group, c is 0 to 50 (average number of moles added)and (R^(3d)O) moles whose number is c may be the same or different. 3.The allergen-reducing agent according to claim 1, wherein thewater-soluble polymer compound comprises unit (a3) of the followingformula (4) and/or the following formula (5) and unit (a4) of thefollowing formula (6) and/or the following formula (7), a molar ratio of(a4)/(a3) is 1/1500 to 30/100 a ratio of (a3) and (a4) in total in themolecule is 50 to 100 mol %:

wherein J and M are a group selected from —O—, —OCO— and —COO—, R^(6a)and R^(7a) are a C1 to C6 alkylene group, R^(6b) and R^(7b) are a C1 toC6 alkylene group, R^(6c) and R^(7c) are a C4 to C30 hydrocarbon groupwhich may be substituted with a hydroxy group, L and Q are a groupselected from —O—, —OCO— and —COO—, and r and s are 0 to 50 (averagenumber of moles added), and (OR^(6b)) moles whose number is r or(OR^(7b)) moles whose number is s may be the same or different.
 4. Anallergen-reducing agent contained in a spray container, which comprisesthe allergen-reducing agent of any of claims 1 to 3 introduced into acontainer provided with a spray device.
 5. An allergen-reducing sheetcomprising a flexible sheet impregnated with the allergen-reducing agentof any of claims 1 to
 3. 6. A method of reducing allergen, whichcomprises spraying the allergen-reducing agent of any of claims 1 to 3into space.
 7. The method according to claim 6, wherein the polymercompound is cellulose, starch or a derivative thereof.
 8. A method ofreducing allergen, which comprises spraying or applying theallergen-reducing agent of any of claims 1 to 3 onto the surface of anobject and then wiping it off with a water-absorbing article beforedrying.
 9. A cleaning method which comprises cleaning by vacuuming orsweeping cleaning after carrying out the method of claim
 7. 10. Acleaning method which comprises wiping the surface of an object with anallergen-reducing sheet having a flexible sheet impregnated with theallergen-reducing agent of any of claims 1 to 3 and cleaning byvacuuming or sweeping cleaning.
 11. The method according to any ofclaims 8 to 10, wherein the polymer compound is cellulose, starch or aderivative thereof.